Struct Chem (2011) 22:717740 DOI 10.

1007/s11224-011-9769-0

REVIEW ARTICLE

Interplay of thermochemistry and Structural Chemistry, the journal (volume 21, 2010) and the discipline
Maja Ponikvar-Svet Joel F. Liebman

Received: 24 January 2011 / Accepted: 16 February 2011 / Published online: 5 March 2011 Springer Science+Business Media, LLC 2011

Abstract In the current review the content of the journal Structural Chemistry for the calendar year 2010 is related to thermochemistry. To a short summary of each article in this volume of the journal a thermochemical comment is added. Keywords Structural Chemistry Thermodynamics Physical Chemistry Thermochemistry Enthalpy of formation Chemical reactions Phase transitions

Introduction The current review of Structural Chemistry for the calendar year 2010 has become tradition as this is already the 10th review and as such, constitutes a jubilee review. Let us add that we have been told that these reviews in which an attempt is made to link experiments and theory of all of the articles in a given chemistry/physics/material science periodical, represents a unique and appreciated approach. This adds to our enthusiasm to continue with this annual project. This review is conceptually and organizationally very much the same as the reviews of previous volumes of this journal [110] in which each article has been reviewed and

summarized by us from our personal perspectives as well as knowledge, facilitated wherever possible by the original authors choice of key words. Of course, our perspectives are often very much different as is also our basic scientic educationit is interesting to observe how scientists working in different areas consider the same subject. Therefore, it is perhaps also educational how we handle the same area of investigation from our perspectives of theoretical and analytical chemistry and then combine the comments into a logical unit. The review is supplemented by adding thermochemical comments. Occasionally, it is found that the investigations presented in the articles document inadequacy of current knowledge by the scientic community and that additional studies enlightening the investigated area would be highly desirable. As such, hints, suggestions, and encouragement for possible future research are often given. Thermochemical data are occasionally given as part of our added material as well. All data for inorganic compounds with otherwise unreferenced enthalpies of formation will be assumed to be taken from the Wagman compendium [11], while corresponding unreferenced enthalpies of formation of organic compounds will be assumed to be taken from the Pedley compendium [12].

Issue 1
M. Ponikvar-Svet (&) ef Department of Inorganic Chemistry and Technology, Joz Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia e-mail: maja.ponikvar-svet@ijs.si J. F. Liebman (&) Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250, USA e-mail: jliebman@umbc.edu

Volume 21 begins with the editorial by Hargittai [13] on Linus Pauling and his work on the structure of proteins and eventual discovery of the alpha-helix. Pauling postulated that the amino acid units are linked to each other in the folded protein molecule not only by the normal peptide bond but also by hydrogen bonding that is facilitated by this folding of the protein. His quantum chemical theory of

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resonance contributed to his understanding of other scientic phenomena, although at the same time, this theory was attacked in Soviet Union as an ideological aberration. In the rst of the theoretical papers that follow Xu and Chen [14] described use of density functional theory (DFT) to predict the structural parameters, IR spectra, and thermodynamic properties of tetrazole derivatives. The total energies, heats of formation, and enthalpies of combustion indicate the following order of stability: 5-(2,4,6-trinitrophenyl)-2H-tetrazole [ [5-(2,4,6-trinitrophenyl)-1H-tetrazole [ [5-(2,4,6-trinitrophenyl)-5H-tetrazole. A similar result is found for the corresponding three isomers of 5-(2,4,6-trinitrobenzyl)-tetrazole. While there is a considerable body of experimental data that allow for the comparison of the stability of 1H and 2H-tetrazoles, we know of no corresponding study for 5H-tetrazoles. Indeed, we know of but few thermochemically relevant studies of species with a N=NN=N substructure. One was the study of species [15] of the type ArN=NN=NAr as part of the comparison of the dimerization of, and N2 loss by, transiently formed ArN2 radicals. Another is the suggestion that 5-nickelatetrazoles may enjoy signicant stability [16]. Liu et al. [17] then used DFT to study the correlation between regioselectivity and site charge in propene polymerization by single-site metallocene catalysts such as [Cp2ZrMe]?. The activation energy for 1,2-insertion was shown to be lower than that for 2,1-insertion in agreement with the experimental data. Let us ask now if there is any steric repulsion between the methyl group of the propene and the cyclopentadienyl rings that contributes to the regioselective addition? How different are the activation energies for Z- and E-2-butene from that of propene wherein this methyl/cyclopentadienyl repulsion in these 4-carbon olens is unavoidable? Chapkanov [18] studied 2-aminopyridinium tetrachlorocuprate (II) salt both in solution and in the solid-state using IR and UVVis spectroscopy 1H-NMR, TGV, and DSC methods. A change of aromatic character was explained by the Npy protonation that leads to weak charge redistribution in the pyridinium ring and thereby changes in geometrical parameters. Thermodynamically, the stability of the aminopyridines decreases in the order 2- [ 4- [ 3- and span a 25 kJ mol-1 range. The proton afnities [19] of the aminopyridines decrease in the order 4- [ 3- [ 2and span a 33 kJ mol-1 range. From these data we nd that the stability of the aminopyridinium ions decreases in the order 2- [ 4- [ 3-. Is this change in enthalpy of formation, and presumably aromaticity, reected in the properties of the corresponding aminopyridinium salts such as the above cuprates? For typical concentrations found in solutions the number the solvent molecules outnumber the solute molecules which makes the analysis of solute molecular structure

difcult. Lee and Ihee [20] used time-resolved X-ray solution scattering for determining structures of small molecules and proteins in solution. The difference scattering curves generally exhibit much higher structural sensitivity to the solute structure than the original scattering curves. The authors discuss solutions of iodine in methanol and dissociation to form atomic iodine. We note that the enthalpy of solution of gaseous I2 in methanol is 54 kJ mol-1; we know of no corresponding data for the atomic iodine as solute. Stem and Ellzey [21] studied organotin(IV) molecules using computational optimization modeling (COM) which enables the prediction of molecular properties and structures. The data were compared to the experimental data as obtained by X-ray crystallography and solid-state NMR. Hyperconjugation-derived stabilization is suggested to be an important force in these molecules. The lack of validation of computational optimization treatments for many organotin(IV) molecules remains a limiting factor against generating accurate COMs. These authors explicitly investigated species with SnS bonds. The enthalpy of formation of the simplest condensed phase species of tin(IV) with sulfur, namely the binary sulde and inorganic material, SnS2 has been reported [22] but comparison with organotin suldes remains unexplored. lu et al. [23] describe synthesis and char leymanog Su acterization, including crystal structure analysis, of 2-propylamino-5-[4-(2-hydroxy-3,5-dichlorobenzylideneamino) phenyl]-1,3,4-thiadiazole. The experimentally determined molecular geometry was compared to the geometry obtained by DFT calculations. The results showed that the Schiff base, which contains a thiadiazole ring, prefers the E-conguration. A thermochemical comparison of 1,2,3-, 1,2,4-, and 1,3,4-thiadiazole, their amino analogs and derived Schiff bases is welcomed. Six new salicylic acid derivatives were prepared by et al. using conventional heating or microwaveDjurendic assisted synthesis [24]. Comparison of structures obtained from X-ray analysis and molecular mechanics calculations for three of these synthesized compounds, N-(2-hydroxybenzoyl)-2,2 0 -bis(2-hydroxybenzoyloxy)diethylamine, 2,20 ,200 -tris(2-hydroxybenzoyloxy)triethylamine and N-phenyl2,20 -bis(2-hydroxybenzoyloxy)diethylamine revealed that the intramolecular hydrogen bonds play an important role in stabilizing the conformation of the molecules. The antioxidant activity and cytotoxicity tests showed strong activity against hydroxyl radical, as well as exhibiting promising lipid peroxidation inhibition. Comparison with the 3- and 4-hydroxybenzoic acid isomers is welcomed: it is to be noted that the enthalpies of formation of the three isomeric hydroxybenzoic acids spans but 6 kJ mol-1 in the solid state. Does this mean the effect of the OH groups on stability and conformation is rather negligible?

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In the experimental paper by Zhang et al. [25] the synthesis and characterization of complex [Co(Imazameth)3] 0.5DMF4H2O (Imazameth = ()-2-(4,5-dihydro-4-methyl4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-5-methyl-3pyridinecarboxylic acid) by IR spectroscopy, elemental analysis, thermal gravimetric analysis, uorescence properties, and single crystal X-ray structure analysis is reported. Octameric water clusters were observed. We know of no direct measurement as to the enthalpy of formation difference of the tautomeric 4,5-dihydro-4(5)-oxo-imidazole and imidazole-4(5)-ol or even between their methylated derivatives [26]: synthetic chemists [27, 28] have provided useful information. In the following experimental study by Kruszynski [29], 2,20 -bipyridine complexation properties of the dichloroacetates of zinc and cadmium is reported. [Zn(C10H8N2) (CHCl2COO)(H2O)3][Zn(C10H8N2)(CHCl2COO)3]? and [Cd(C10H8N2)2(CHCl2COO)2] were synthesized and characterized by elemental and thermal analyses, IR and UVVIS spectroscopy, and crystal X-ray structure analysis. The zinc compound is a rare example of a salt containing complex anions and complex cations in which the same organic ligands and anions are in the inner coordination spheres. Consider now Zn(C10H8N2)(CHCl2COO)2(H2O)2 [30]. Forgetting now the differences of Zn and Cd, do the three compounds in this paragraph compose a homologous series of hydrates with regards to nearly constant enthalpy of formation differences, cf. [31]? Using the MP2 method Qiu et al. [32] studied hydrogen bonding patterns of the base pairs between 4-thiouracil, analogue of uracil and four RNA bases, adenine, uracil, guanine, and cytosine. The order of stability is s4U : guanine [ s4U : adenine [ s4U : uracil * s4U : cytosine and the calculated interaction energies for the complexes vary from -7.4 to -13.3 kcal mol-1. What about the difference of their interaction energies with other nucleobases? What is the enthalpy of formation difference of 4-thiouracil and the isomeric 2-thiouracil? Tomura and Yamashita [33] successfully synthesized the 2:1 co-crystal of 1,2,5-thiadiazole-3,4-dicarboxylic acid and 4,40 -bipyridine, which has been widely used as a ligand in supramolecular architecture in crystal engineering. A unique two-dimensional ladder-type molecular network in the co-crystal is built using intermolecular OHN hydrogen bonds and SO heteroatom interactions. The 1,2,5-thiadiazole ring is expected to be aromatic by the criterion of having 6 p electrons. Comparison of the aromaticity of its ring annelated qunoxaline and dihydroquinoxaline derivatives has recently been reported [34]. How do these species compare with the parent 1-ring heterocycle? Gossypol is a polyphenolic terpene that is found in the cotton plant. Four new solid-state forms, two polymorphic and two solvated, of the likewise naturally occurring

derivative, 6,60 -dimethoxygossypol were synthesized and their structures determined by X-ray diffraction by Zelaya et al. [35]. We note that gossypol and its dimethoxy derivative may be recognized as 2,8-dihydroxy-1-napthaldehydes. What is the enthalpy of formation difference between the aldehyde hydrogen-bonded species involving the 2-hydroxy group and the ring closed lactol isomer formed with the 8-hydroxy? In the following study, Qi et al. [36] studied the silylenoid 2-NH2CH2C6H4(CH3)SiLiF using DFT to get more insight into the structures, and properties and solution phase reactions of pentacoordinate silylenoids. 2-NH2CH2 C6H4(CH3)SiLiF is more stable than corresponding silylene NH2CH2C6H4(CH3)Si. The insertion of 2-NH2CH2 C6H4(CH3)SiLiF into CF bonds is similar to that of NH2CH2C6H4(CH3)Si. The activation barrier for the former is 62.9 kJ mol-1 higher than that for the latter. What are the corresponding values for the 3- and 4-isomers of NH2CH2C6H4(CH3)SiLiF and the corresponding silylene, and what are the differences of enthalpies of formation within sets of isomers? Trzesowska-Kruszynska [37] synthesized, characterized by spectroscopic and thermogravimetric analyses, and determined the crystal and molecular structures of N-(2-carboxyphenyl)-4-dimethylaminebenzylideneimine pentahydrate, which is an example of Schiff base compound existing as the zwitterion, stabilized by the intramolecular N?HO- hydrogen bond. As shown by NBO analysis this form is energetically unfavorable for the free molecule but in the solid and solution states the intermolecular interactions support the presence of the zwitterionic form. How many waters are needed to stabilize the zwitterionis it necessarily at least ve? In the theoretical study by Macaveiu et al. [38] the effects of NO2 groups on intramolecular interactions were studied using chloromethane, ClCH3. NO2 groups were successively introduced to form chloronitromethanes. Corresponding CN and F derivatives were also checked. Shortening of the carbonchlorine bond in chloronitromethanes was explained by the changes in the attractive ClO electrostatic interactions. Following up on this investiga tke and Liebman [39] tion of chlorotrinitromethane, Klapo studied the energetics of chlorotrinitromethane and other trinitromethyl derivatives. Ghosh et al. [40] synthesized mononuclear nickel(II) and copper(II) complexes with the tetradentate Schiff base biacetyl bis(benzoylhydrazone) (H2babh) with the general formula [M(babh)] and characterized them by microanalysis, magnetic susceptibility, spectroscopically, and X-ray crystal structure analysis. Both compounds form onedimensional self-assemblies via pp interaction and hydrogen bonding. Considering the partial double bond character of amides, the above species are seen to have four

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contiguous p bonds not counting the terminal benzene rings. What is their conjugation energy? In the next article, Khalaji et al. [41] report the synthesis of the Schiff base 6-[(5-bromopyridin-2-yl)iminomethyl]phenol, and additionally characterized this species by elemental analysis and spectroscopic methods. X-ray crystal structure analysis showed a monoclinic structure. DFT analysis showed that conformer in which the hydroxyl group and imine nitrogen participate in an intermolecular hydrogen bonding and pyridine nitrogen is in the other side of the N1C7 bond is the most stable of four isomers. How are the relative isomer stabilities modulated by 5-substituents, such as bromine in the current species? An et al. [42] in their study describe thermal synthesis, characterization, and crystal structures of 3-D supramolecular compounds [Co(phen)(tdc)(H2O)3]5H2O and [Co (phen)(Htdc)(H2O)3](Htdc)2H2O (phen = 1,10-phenanthroline, H2tdc = thiophene-2,5-dicarboxylate). While in the former compound water layers were found to enable overall 3-D supramolecular architecture by H-bond interactions, they were not observed in the latter compound. What is the equilibrium constant of the reaction Cophen tdcH2 O3 5H2 O H2 tdc , CophenHtdcH2 O3 Htdc 2H2 O 3H2 O 1 In the following paper, Ye et al. [43] report on the synthesis of four new lanthanide complexes (Ln(3,4-DMBA)3 phen)2 (Ln(III) = Nd, Sm, Tb, Dy, 3,4-DMBA = 3,4dimethylbenzoate, phen = 1,10-phenanthroline). Compounds were characterized by elemental and thermal analyses, IR spectroscopy and X-ray crystal structure analysis. Kinetic and thermodynamic parameters were calculated which reveal that the decomposition of the complexes is not spontaneous. Four of fourteen lanthanides are discussed above. What periodic trends would be exhibited for these kinetic and thermodynamic parameters had all these lanthanide species were to be studied? Using DFT and Baders theory of Atoms in molecules (AIM) theory Maecka [44] investigated the nature of resonance-assisted NHO hydrogen bonds for 3-aminomethylene-2-methoxy-5,6-dimethyl-2-oxo-2,3-dihydro2k5-[1,2]oxaphosphinin-4-one and its derivatives at the bond critical points. Analysis of the ellipticity parameters indicated p-delocalization over all six ring atoms. How is this delocalization manifest in terms of resonance stabilization? We note that there are no thermochemical data for any [1, 2]phosphinin derivative. Obtaining single crystals suitable for single crystal X-ray crystallography of bile acid derivatives is difcult. Ahonen et al. [45] studied solid state structures of lithocholyl-N-(2-aminoethyl) amide. One pure polymorph along

with four solvates were isolated. 13C and 15N CP/MAS NMR and powder X-ray diffraction (PXRD) was a useful structural determination strategy. We note few determinations of the enthalpy of few steroids have been made. Does this mean that samples for calorimetry are likewise hard to nd? More precisely, the thermochemical review by Domalski [46] gives a collection of results but the later compendium, our organic archive by Pedley, inexplicably fails to include most of these data. As part of the study toward extraction of heavy metals and the inclusion of diorganodithiophosphates in activated composite membranes (ACM) as carriers in the selective rez-Garc a et al. [47] synthesized transport of mercury, Pe and characterized ve Sn-alkyl (O,O0 )-diorganodithiophosphates RS2P(OC6H4)2. Structure elucidation showed that the crystal packing of these compounds is stabilized by cation-p, weak hydrogen bonding CHO, as well as aromatic non-bonded interactions. What is found for the isomeric RO2P(SC6H4)2 derivatives and both of the mixed O- and S-alkylated RO(S)P(OC6H4C6H4S) and RS(O)P(OC6H4C6H4S) species. Indeed, what are the relative stabilities of the various isomers? Theoretical work by Liu et al. [48] is aimed toward investigation of bonding character of noble-gas compounds of the type CH3NgF (Ng = He, Ar, Kr, or Xe) at the MP2 level of theory. NgF bond lengths of the CH3NgF species are all longer than those of the corresponding HNgF species and infrared intensity of the CNg and NgF stretching vibrations are larger than that of the other vibrations. The AIM analysis indicated that the NgF bond (Ng = He, Ar, or Kr) bonds are dominated by electrostatic interaction and the two CNg (Ng = Ar or Kr) bonds by covalent interaction. The bond length analysis seems to indicate that both the NgF and the CNg bonds are dominated by covalent interaction. No CH3NgF have yet been observed. However, except for Ng = He, all the related CH3Ng? are known from experiment and indeed, their CNg bond energies have been determined [49, 50]. The following paper by Wang et al. [51] deals with the synthesis and characterization of new silver coordination polymers with high packing coefcients. Reactions of silver squarate, including a new polymorph, and silver tartrates with pyrazine resulted in three products which have been structurally characterized. The crystal structures and the space-lling properties with respect to the information retrieved from the Cambridge Structural Database (CSD) are discussed. The enthalpy of formation of silver squarate has been determined [52]; now, how we appraise the aromaticity of this species with its 2 p-electron anion [53] especially confounded because of the presence of the Ag? counterion?

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Avc et al. [54] compared results of HartreeFock (HF) and DFT for computed and experimental IR vibrational frequencies and chemical shifts of 3-[(1E)-N-ethylethanimidoyl]-4-hydroxy-6-methyl-2H-pyran-2-one. The B3LYP DFT studies, which include the effects of electron correlation, show a better t to the experimental vibrational frequencies and 13C NMR chemical shifts than those using HF. We recognize this species as the N-ethylamide of dehydracetic acid, a highly substituted pyrone. No enthalpies of formation of either 2- or 4-pyrone, or any simple derivatives, have been determined experimentally to compare with recent high level theoretical predictions [55]. We note the enthalpy of dimerization of diketene to dehydracetic acid has been measured [56], but as we said the latter species is highly substituted and therefore, comparisons are problematic [57]. In the theoretical work by Oliveira et al. [58] DFT was used to study trimolecular properties of bifurcated BeH22HX and linear HXBeH2HX dihydrogen-bonded complexes with X = CN and NC. The geometries of these systems are well-dened wherein the linear complexes present shorter dihydrogen bond distances and the bifurcated complexes present the larger ones. Vibrational effects were interpreted by the quantum theory of atoms in molecules (QTAIM) parameters. We may ask what is the difference of the enthalpies of formation of the ligating HCN and HNC; only once answered should we ask about the above beryllium complexes later. Ionmolecule reactions result in ca. 75 kJ mol-1 [59, 60], to be compared with the calorimetrically determined 90 kJ mol-1 for CH3CN and CH3NC, and 63 kJ mol-1 for 2,4,6-(CH3)3C6 H2CN and its corresponding isonitrile [61]. A series of experimental papers then follows. As little is known about multiple bonds linking two reactive centers Kassaee et al. [62] continued their related investigations using DFT on unstable and experimentally difcult to obtain the (nitrenoethynyl)halomethylenes, NC:CCX (X = H, F, Cl, Br). Triplet minima are 5456 kcal mol-1 more stable than their corresponding quintets. No reactive intermediate is observed through connecting singlet states of carbene and nitrene subunits and show about 70 kcal mol-1 greater stability than the corresponding triplet states. We recognize these species as excited states of cyanoacetylene and its substituted derivatives. An enthalpy of formation of ca. 85 kJ mol-1 has been reported in the ion molecule literature [63] for cyanoacetylene itself, very discrepant from a value by interpolating those calorimetrically determined for acetylene and dicyanoacetylene. So, is this value for cyanoacetylene correct? Not enough is known about the thermochemistry of cyanoacetylenes and the isomeric polyacetylenes to appraise this. Lu et al. [64] studied rarely investigated complexes that contain an asymmetrically 3,5-disubstituted 1,2,4-triazole. Syntheses, characterization, and single crystal structures of

trans-[CuL2(ClO4)2] and cis-[CoL2(H2O)2](ClO4)2H2 OCH3OH (L = 3-methyl-4-(p-bromophenyl)-5-(2-pyridyl)-1,2,4-triazole) which have a similar pseudo-octahedral [MN4O2] core, two ClO4 ions in the trans position in the former and two H2O molecules in the cis arrangement of the latter compound. What are the respective cistrans isomerization enthalpies and why are they of opposite sign? In the next paper, Eimann et al. [65] report syntheses and X-ray crystal structure analyses of 5-iodocytosine and of three different derivatives of bromo substituted nucleosides. The packing structures reveal aggregations created via networks of hydrogen bonds involving NHN, NHO, and OHO interactions between the nucleobase and ribose units. A further support stems from weak CHO contacts. These species all contain C, H, N, O, and either I or Br. We know of comparatively few species with C, H, N, O, and Br for which the enthalpy of formation is known, e.g., bromotrinitromethane [66] and 5,7-dibromo8-hydroxyquinoline [67], and with C, H, N, O, and I, the iodo analog of these species, respectively [66, 67]. Other species are the parent and n-butanoate of the two 3,5-dihalo-4-cyanophenols [68]. Then Ji et al. [69] describe the synthesis, characterization, and crystal structures of [Cu2(HL)2](ClO4)26H2O and [Zn2(HL)2](ClO4)22H2O (H2L = di(2-pyridylcarbaldehyde)-6,60 -dicarboxylic acid hydrazone-2,20 -bipyridine) which revealed to be bimetallic molecular squares. We know of no enthalpy of formation data for any bipyridine carboxylic acid derivative; by contrast this quantity has been determined for several biphenyl carboxylic acid derivatives [70] including the 2,20 -dicarboxylic acid anhydride [71]. Lah and Leban [72] show in their study on the syntheses and crystal structures of three new Cu(II) complexes comprising three simple pyridine alcohol ligands, 3-pyridinepropanol, 2-pyridineethanol, and 2-pyridinemethanol in their neutral forms. This study documented considerable structural diversity within the system limited to simple pyridine alcohols and Cu(II) halides. The solution phase complexation enthalpy of Cu(II) with the latter two alcohols has been directly determined [73]; we know of no such measurement for the rst species. The sole enthalpy measurement we know of for this species is that involving its intra- and intermolecular hydrogen bonding, a study that involves the other two pyridine alcohols as well [74]. et al. [75] describe the syntheses, characterizaStyczen tion, and crystal structures of manganese and cobalt tetrabromometallates(II), [(C2H5)4N]2[CoBr4] and [(C4H9)4 N]2[MnBr4]. Magnetic measurements suggest weak antiferromagnetic intermolecular interactions between the divalent metal ions in the crystal lattice. Consider tetraethylammonium and tetrabutylammonium halides. There is a nearly constant 200 kJ mol-1 difference for the enthalpies of

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formation of these chlorides, bromides, and iodides. Is the difference (per cation) found for the above tetrabromometallates affected by this antiferromagnetic coupling? kely et al. [76] The issue closes with the paper by Sze who studied crown ethers containing an alkyl diarylphosphinate or diarylphosphinic acid unit. Crystals for X-ray analysis of the achiral and chiral methyl phosphinates as well as the achiral phosphinic acid which was found to form hydrogen bonded dimers in the crystal were successfully prepared. The calculated electronic circular dichroism spectrum shows a reasonable agreement with the spectra obtained in solution which shows that the structure observed in the crystal is predominant in solution as well. The thermochemistry of organophosphorus compounds has been largely ignored when compared to that of sulfurcontaining species; indeed, the Pedley archive includes none of the former data, Domalskis compendium [46] but a few. We note that the enthalpies of formation of phenylphosphinic, diphenylphosphinic, and phenylphosphonic acids have been measured [77].

Issue 2 This issue is devoted to the Polish chemist Adam Bartecki on the occasion of his 90th birthday. The rst paper is an lak-Golonka [78] who gives a short editorial by Cies introduction on the work of Adam Bartecki whose interests range from coordination chemistry to practical applications, where especially worth mentioning is his expertise in electronic spectroscopy and his successful work on color. Following is a paper by Warnke et al. [79], who report on the synthesis and crystal structure of the new Fe(III) complex [(C2H5)4N][FeCl4] crystallizing in the hexagonal system. The magnetic susceptibility measurements revealed suggests weak antiferromagnetic coupling. Results of electron paramagnetic resonance spectroscopy indicate symmetric arrangement of the chloride ligands in the coordination sphere of Fe(III). The enthalpies of formation of (C2H5)4NCl, KFeCl4 and KCl are well-established; that of [(C2H5)4N][FeCl4] remains unknown. We wonder how close to thermoneutral is the following solid state exchange reaction C2 H5 4 NCl KFeCl4 ! KCl C2 H5 4 N FeCl4 2 The related halogen exchange reactions (X = Br, I) C2 H5 4 NCl KX ! KCl C2 H5 4 NX 3 are exothermic by ca. 20 and 40 kJ mol-1, respectively. In the next paper, Grifths et al. [80] describe catalystenhanced molten salt oxidation, which is an extension of molten salt oxidation originally employed in the 1960s. As

revealed, by addition of nitrate catalyst the concentration of the oxidizing species, superoxide, and peroxide ions that are produced from the oxygen entering the carbonate melt could be increased and maintained. Further characterization of possible adducts between nitrate and nitrite with oxygen and peroxide has been done by employing DFT. While the enthalpy of formation of peroxynitrate and its covalent hydrogen and alkyl derivatives has only now been understood [81], the enthalpy of formation of peroxynitrite ion is solidly established [82]. Radecka-Paryzek et al. [83] synthesized, characterized, and determined the X-ray crystal structure of 2,6-diacetylpyridinediphenylhydrazone perchlorate. Spectroscopic and analytical data of its chelating behavior toward lanthanum(III), praseodymium(III), and neodymium(III) showed 1:2 metal to ligand stoichiometry. What are the relative stabilities of the isomeric diacetylpyridines? Is it the same order as recently found for the related pyridinedicarboxylic acids [84] wherein COOH replaces COCH3? The enthalpies of formation of the three monoacetylated pyridines have all been reported [85]. As showed in the study by Staszak et al. [86] 3-methyl4-nitropyridine-N-oxide (3-mnpn) interacts with copper(II) acetate to form a solid, crystalline, dinuclear copper(II) complex with formula [Cu(OAc)2(3-mnpn)]2. New bands observed at 16000 and 24000 cm-1 in the electronic spectra were plausibly ascribed to metalmetal interactions and solid state effects. We wonder how different are the spectroscopic and thermochemical properties of 3-methyl4-nitropyridine-N-oxide and 4-methyl-3-nitropyridine-Noxide, and of related complexes; the enthalpy of formation of only the former N-oxide is available from the literature [87]. Phenytoin complexes of Co(II) and Ni(II), [Ni(H2O)4 (pht)2] and [Co(H2O)4(pht)2]1.5NH3H2O (pht = phenot ska-Tuszkanow oinate anion) were synthesized by Puszyn et al. [88]. The compounds were characterized by spectroscopic, thermal, and magnetic measurements. X-ray structural analysis revealed that the environment around the nickel and cobalt ions can be described as a distorted octahedron. Although the rst measurement of the combustion enthalpy of a hydantoin (5-ureidoimidazolin-2,4dione, the so-called allantoin) was rst reported over 100 years ago [89] that of phenotoin (the 5,5-diphenylderivative) remains unmeasured despite its biomedical importance. The thermochemistry of hydantoins remains problematic [90] and incompletely studied. Nowak et al. [91] report the synthesis of several new compounds of the avonoid, rutin, with Fe(II) and Fe(III) ions. This study gains relevance because selective inhibitory effect of rutin under pathologic conditions induced by iron overload is thought to be due to the formation of inactive ironrutin complexes. Complexes having

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formulas FeOH(C27H29O16)5H2O, Fe2OH(C27H27O16)9H2O, Fe(OH)2(C27H29O16)8H2O, [Fe6(OH)2(4H2O)(C15H7O12)SO4]10H2O were synthesized. Their composition was determined by elemental analysis and thermogravimetric measurements. These species were additionally characterized by spectroscopic and magnetic properties. A thermodynamic study of metal-avonoid interactions has been reported [92]. In the next paper, Adach et al. [93] report synthesis, characterization, and X-ray crystal structure of a novel cobalt(II) complex [Co(L)Cl]2[CdI4] (L = tris(1-(3,5dimethylpyrazolylmethyl)amine) obtained in situ from the redox system (Co0, CdCl2, NH4I, 1-hydroxymethyl-3,5dimethylpyrazole). Diverse isomers exchanging the halogens Cl and I may be suggested: what determines the formation of the above iodocadmate? We do note that the solid state reaction CoI2 CdCl2 ! CoCl2 CdI2 4

is exothermic by ca. 45 kJ mol-1 suggesting [Co(L)Cl]2 [CdI4] is plausibly more stable than [Cd(L)Cl]2[CoI4]. However, this ignores all contributions from metal-N bonding. Wojciechowska et al. [94] reported the new crystalline Cu (II) complex Cu(phen)2OCrO3](phen)0.54H2O, derived from the [Cu(II)-phen-K2CrO4] system (phen = 1,10-phenantroline) system. The compound was characterized by spectroscopic (NIRVisUV) methods and its structure determined by X-ray diffraction. The chromate unit was found to be monodentate. Consider now the simpler, i.e., uncomplexed, CuCrO4. Comparison of its enthalpy of formation with the other mixed copper chromium oxides, Cu2Cr2O4, and CuCr2O4 [95] is welcomed; a study of their Gibbs energies has been reported [96]. In the study by Kamecka et al. [97] systems Cu(II)L1L2 (L1 = ethylenediamine (en), diethylenetriamine (dien) or N,N,N0 ,N0 ,N00 -pentamethyldiethylene triamine (Me5dien) and L2 = (aminomethyl)phosphonic acid (glycinephosphonic acid, Gly(P)) were investigated using potentiometric, spectrophotometric, and EPR methods. The EPR parameters obtained correspond to a ve-coordinate species. The enthalpies of formation of ethylenediamine, diethylenetriamine [98, 99], and triethylenetetramine [98] have all been determined as well as that of tetraethylenepentamine [100], the last value should solvation enthalpies be ignorable. As part of continuing investigations on interpretation of the electronic spectra of the copper(II) complexes with niarska-Biernacka [101] Schiff bases, Kurzak and Kuz synthesized the bis(salicylidene-2-amino-3-methylpyridine) copper(II) complex, which was characterized by elemental analysis, conductivity measurements, and UVVis spectroscopy. Coordination properties of donor atoms and their

bonding abilities, as well as solvatochromism were studied by electronic spectra. The angular overlap model (AOM) calculations were carried out within the framework of the simplest model. Colorimetry and calorimetry have occasionally been combined to enhance understanding of solvatochromic systems, e.g. [102]. Further Radtke et al. [103] describe synthesis, spectral characterization, thermal properties, and X-ray crystal structures of the novel Zr(IV) b-ketodiester complexes of general formulas [Zr(dtbacdc))4], [Zr(dmacdc)3(OiPr)]2, and [Zr(dtbacdc)3(OiPr)]2 (dtbacdc = di-tert-butyl-1,3-acetonedicarboxylato, dmacdc = dimethyl-1,3-acetonedicarboxylato ligands). As the synthesized compounds have potential application in the technique of chemical vapor deposition, the most often used method in the preparation the high quality of ceramic materials and thin metal oxide layers, thermal decomposition pathways were discussed. The enthalpies of formation of the related homoleptic 8-coordinate zirconium complexes with acetylacetone and its 1,1,1-triuoro derivative have been reported [104]. With interest in cobalt(II) complexes with tetrahedral or pseudo-octahedral geometries with Schiff bases derived from salicylaldehyde and amines in a variety of solvents, Kurzak et al. [105] prepared [Co(sap)2] (Hsap = salicylidene-2-aminopyridine) and characterized it by elemental analysis, molar conductivity, cyclic voltammetry, and Vis NIR spectroscopy. A tetrahedral geometry was suggested in the solid state and in solution. Electronic spectroscopy was used to study the ligandeld parameters and solvatochromism. The authors describe electrochemical reduction and the addition of the electron to the metal and pyridine ring. What does that tell us about the conjugation of the endo and exocyclic nitrogens? The thermochemistry of 2-aminopyridine metal complexes has been explored, e.g., the enthalpy of formation of bis(2-aminopyridine)zinc chloride has recently been reported [106] . Zeolites or related materials have been widely used as catalysts, cation exchangers, and adsorption media. In the paper by Roth and Dorset [107], it is shown that the symmetry principles may govern and rationalize formation of different zeolite frameworks from corresponding layered zeolite precursors. Despite their seeming complexity as dened by the large number of atoms per formula unit, enthalpies of formation of zeolites are encouragingly wellunderstood [108]. With the purpose to provide better understanding of the interactions between explosives and surfaces of selected porous metalorganic frameworks that possess the catalytic activity, Petrova et al. [109] theoretically studied the interactions between the adsorption of 1,3,5-trinitro-s-triazine (RDX) and triacetone triperoxide (TATP) on representative fragments of metal organic framework (IRMOF-1). Comparison of these species with their respective

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oligomers is welcomed: we note the enthalpies of formation of RDX and the corresponding tetramer (HMX) are both known. The value for neither TATP nor for the corresponding dimer, tetramethyl-1,2,4,5-tetroxane, are known from experiment. However that of several other tetroxanes such as the parent species [110], and the 3,6-bis(butanal) [111], 3,6-bis(butanoic acid) [112] and 3,6-diphenyl [113] derivatives have been reported. _ dz _ ewski et al. [114] reexamined the X-ray crystal Droz structure of bis(4-hydroxybenzhydrazide)copper(II) sulfate dihydrate complex. The two water molecules are not coordinated to the metal, but rather stabilize the sulfate group orientation and link the layers of complex molecules by strong hydrogen bonds. DFT calculations were used to interpret IR and Raman spectra that had been enhanced by deuteration and copper stable isotope substitutions. Copper (II) sulfate exists as the anhydrous and the mono-, tri-, and pentahydrateso, why not also the dihydrate [115] here as well? New mixedligand lanthanide complexes of Er(III), Yb(III), and Lu(III) with 4,40 -bipyridine and dichloroacetates were prepared by Czylkowska et al. [116]. X-ray crystal structures of the complexes were determined as well as elemental, IR spectroscopic analysis, conductivity measurements, and thermal studies (TG-DTA-DTG) were performed. The intermolecular OHO, OHN, CHO, CHCl, and p p interactions link complex and organic molecules to the three-dimensional network. The relative acidity of haloacetic acids, e.g., dichloroacetic acid, or conversely, the relative basicity of haloacetate anions is an exemplary exercise in the relative importance of substituent steric and inductive effects and solvation energies of ions and related neutrals [117, 118]. How are complexation energies and enthalpies of the diverse haloacetates affected by halogens? Kulesza et al. [119] synthesized the new neodymium(III) complex NaNd(SP)4 chelate (SP = C6H5S(O)2NP(O) (OCH3)2) and determined it X-ray crystal structure. Large intensity of the 4I9/2 ? 4G5/2; 2G7/2 transition with a relatively high symmetry has been found. The high-resolution absorption, emission, and excitation spectra and accompanying crystal-eld calculations have been performed and compared with the earlier reported compound NaNdWo4H2O (Wo = CCl3CONP(O)(OCH3)2)). We know of no enthalpy of formation data for any acylphophoramide; indeed, the only phosphoramides with known enthalpies of formation are the parent species P(O)(NH2)3 [120] and the alkylphosphonic dianilides, CH3P(O)(NHC6H5)2 and C2H5P(O)(NHC6H5)2 [121]. Likewise, we know of only one unequivocal example of the enthalpy of formation of an acylsulfonamide, namely that of saccharin [122]. The general pattern of solvatochromic behavior for a variety of iron(II) complexes has been documented by Burgess and Hubbard [123]. The emphasis of this study was

diimine complexes and their behavior in a variety of ternary aqueous solvent media. Enthalpy and entropy changes associated with the redox chemistry of two different types of iron diimine complexes have been reported [124, 125]. ski then _ dz _ yn Two contributions by Sobczyk and Droz follow. In the rst contribution [126] U(III)-doped LaBr3 single crystals were synthesized and their high-resolution low temperature emission spectra were studied. The emission from the 2K15/2, 2H11/2, and 4F9/2 levels to the ground state, 4I9/2, and from 2K15/2 to the rst excited state 4I11/2 have been investigated and discussed with respect to vibronic transitions. The assignment has been proposed. In the following contribution [127], synthesis of U(IV)-doped KPb2Cl5 single crystal and its unpolarized absorption, excitation, and emission spectra studied. Good agreement was found between theoretical lifetimes calculated by JuddOfelt intensity analysis of 5f25f2 transitions calculated and experimentally measured for this compound. Here are U(III) and U(IV)can U(II) be likewise studied? U(II) has been observed in alkaline earth halide matrices [128] and in salt melts [129] for which a redox potential, and hence a Gibbs energy from the Nernst equation, has been assigned. The last paper in this issue is by Godlewska et al. [130], who studied IR and Raman spectra of Dy, Ho, Er, and Lu phthalocyanine of the type PcLn(OAc). The changes of the structure and symmetry of the axially substituted metallophthalocyanine complexes have been checked and discussed on the basis of group theory. As concluded, this analysis can assist in gaining information on the molecular structure of this type of compounds. How strong is the LnO bond? We wonder about the stability of divalent PcLn species formed by the formal cleavage of the bond, and are they better described as PcLn(III). After all, Pc2Ln species have been studied as neutral species and as radical cations and anions. When do they contain trivalent lanthanides [131]?

Issue 3 Issue 3 of 2010 review opens with the obituary written by Hargittai [132] for Lev V. Vilkov (19312010), a premier scientist interested in the structures of relatively small organic molecules and the techniques capable of this determination. Following this essay, Hargittai [133] wrote an obituary for Torvard C. Laurent (19302009). Laurent was an expert in X-ray diffraction technique of macromolecular structures that led him to do the pioneering research on the structural chemistry of hyaluronan. He determined many of the physicochemical properties of hyaluronan and their relationship to the versatile biological functions.

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In the next contribution, Notario et al. [134] discuss the enthalpy of formation of acrylonitrile, which despite the industrial importance of this species, is still not accurately known from experiment. Using dening reactions, G2 and G3 quantum chemical calculations, and using literature sources, values between 185 and 191 kJ mol-1 were suggested with a recommended average of (188 7) kJ mol-1. A delocalization stabilization energy of but 4 kJ mol-1 has been suggested, a small value in accord with the value for acrylic acid earlier discussed by these authors [135]. Using one- and two-dimensional NMR spectroscopy Silva et al. [136] completed the 1H and 13C NMR signal assignments for four luminescent 1,2,4-oxadiazole containing light-emitting liquid crystals. Experimental chemical shift calculations were in rather good agreement with the signals as calculated by DFT incorporated with GIAO. The thermochemical literature of 1,2,4-oxadiazoles and their 1,3,4- and 1,2,5-isomers is surprisingly rich albeit seemingly only for solid state species. We note that the enthalpies of formation of the diphenyl derivatives of these three heterocycles span a ca. 160 kJ mol-1 range. Organophosphorus inhibitors are among the most dangerous compounds developed by man as they inhibit acetylcholinesterase (AChE). Post-treatment regimens involve also rska-Stania et al. [137] synoxime AChE reactivators. Sko thesized (E)-1,4-bis(4-hydroxyiminomethylpyridinium)but-2-ene (K075) and 4,40 -bis(hydroxyiminomethyl)-1,10 (1,4-phenylenedimethyl)-bispyridinium (K114) bromides and determined their structure by X-ray single crystal analysis. Hydrogen bonds were shown to be of considerable importance in stabilizing these crystals and in the reactivation of AChE. Despite their importance, enthalpies of formation data for oximes is scarce and generally not particularly reliable [138]. [139] prepared the solvated form of and Mahe Nicola biclotymolN,N-dimethylacetamide 1:1 solvate and determined its crystal structure, which was then compared to the crystal structures of the DMSO and DMF 1:1 solvates of biclotymol. Two conformers have been observed experimentally although conformational analysis conducted by employing semiempirical and ab initio techniques of the isolated biclotymol molecule revealed that there are six possible conformers. Biclotymol is a p-chlorophenol derivative. The enthalpy of formation of both m- and p-chlorophenol has been determined; surprisingly, there are no such data for the o-isomer given there are also measurements for all six dichlorophenols [140]. We know of no data for the enthalpy of formation of any of their solvates. a k et al. [141] determined crystal structures of two Hus new polymorphs of simvastatin, a drug for the treatment hypercholesterolemia, by X-ray powder diffraction and

solid-state NMR spectroscopy. The main differences among three polymorphs, the two new and the one earlier described, is only in the O4C20C21C22 and C20C21 C22C23 torsion angles describing the rotation of the side group. It is interesting to note that the phase changes are fully reversible. Simvastatin is a hexahydronaphthalene derivative. The relative enthalpies of formation of the parent hexahydronaphthalenes have been studied [142, 143]; we know of no analogous relative biomedical activities of their analogous simvastatin isomers. Due to the interest in the IIVI semiconductors Xu et al. [144] studied CdTe nanocrystals by DFT. After optimizing Cd3Te3, (Cd3Te3)2, (Cd3Te3)3, and Cd4Te4 structures TeCdligand clusters were optimized to further discuss the bond and optical spectrum qualities of CdTe nanocrystals. The sublimation enthalpy of CdTe and other group 12 chalcogenides was recently explained in terms of atombased thermochemistry [145]. Ponikvar-Svet et al. [6] in the next paper relate thermochemistry to the content of the articles contained in Structural Chemistry for the year 2005 and so this paper represents a conceptual ancestor of the current study. The Kuhn segment, varying in polyheteroarylenes from to ?, links the geometric structure of a 10 to 15 A monomer unit of polyheteroarylenes to its physical properties. In the paper by Ronova [146], a volume factor that serves as a good proxy for the geometric structure of a unit of aliphatic polymers has been suggested. This factor correlates with those physical properties that depend on the free volume. The simplest polyarylene is polyphenylene, (C6H4)n. The enthalpies of formation of the p-isomer [147] and its monophenylated derivative have been determined [148]. The family of plants known as Clusiaceae (Guttiferae) shows a diversity of metabolites, such as oxygenated xanthones which have been widely studied due to their potential a et al. [149] managed to isobiological activities. Corre late 1-hydroxyxanthone, 1-hydroxy-7-methoxyxanthone, 1,5-dihydroxy-3-methoxyxanthone, and 1,7-dihydroxy-3,8dimethoxyxanthone, to determined their X-ray crystal structures and study molecular interactions. Important bonding is represented by hydrogen bonds and the crystal self-assemblies are kept together by pp interactions. While the enthalpy of formation of the parent species xanthone has been determined multiple times [150152], we know of no measurements at all for the above (or for that matter, any)substituted derivatives. Huang et al. [153] studied the nature of hydrogen bonds through structures, energies, frequencies, and electron density topological analysis in (CH3OH)n (n = 28) clusters using DFT, natural bond orbital (NBO), and QTAIM approaches. The strengths of OHO H-bonds in (CH3OH)n clusters increase from n = 2 to 8, along with the increasing

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of DEprep (the amount of energy required to deform the separate bases from their free monomer structure to the geometry that they acquire in the pair cluster) due to the deformations during the formations of clusters. At what stage does the cluster become effectively indistinguishable from the bulk liquid? From the bulk solid? Using DFT approach, Contreras et al. [154] studied nitrogen-containing exohydrogenated carbon nanotubes formed by covalently arranging 210 and 20 layers of identical cyclic units having a pyrimidine backbone. Structural and electronic properties were investigated. Calculated band gap values were small (around 0.2 eV) for all the studied structures and were dependent on the number of layers and the congurations. Recently, the energetics of carbon nitrides (and carbon oxides) was discussed [155]: no thermochemical data yet exist for these nitrogenated carbon nanotubes. Geometric and electronic changes of a series of poly(carbosilysilanes) induced by varying the size and species of the substituting groups was investigated by Ding et al. [156] using DFT combined with AM1 method. While the bias-trans conformation is preferred if the side chain contains fewer than three carbons, the all-trans conformation with a loose-helix backbone is a preference with more than four carbons in side chain. The enthalpy of formation of solid SiC is well-established. How does this number relate to enthalpies of formation for these polymers and discrete organosilicon compounds such as the methylated silanes? In the theoretical paper by Kassaee et al. [157], DFT was used to investigate the effects of different sized rings (cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl substituents) on the stability of spirocyclic (alkyl)(amino)carbenes (CAACs). The cyclopropyl-substituted CAAC shows higher DEs-t and DEHOMO-LUMO than the others (54.2 and 116.7 kcal mol-1, respectively). The ring inversion energy barriers were assigned which do not show a considerable difference with those of the bare cyclohexane, cyclopentane, and cyclobutane; enthalpies of formation are known for these cycloalkanes but none of these carbenes derivatives. In the experimental paper by Prathapachandra Kurup et al. [158] synthesis and characterization including the X-ray crystal structure determination of oxovanadium(IV/V) complexes of 2-hydroxyacetophenone-3-hydroxy-2-naphthoylhydrazone (H2L) along with the crystal structure of an oxovanadium(V) complex [VOL(OCH3)] existing in two polymorphic forms is reported. Consider the related VOL(OH) complex. What is the gas acidity of this species? On which oxygen does VOL(OH) protonate and what is the corresponding gas phase basicity? The enthalpy of formation of aqueous VO2? and VO2? are well-established. Using single crystal X-ray analysis and quantum chemical calculations Fukin et al. [159] analyzed the basic

geometrical, kinetic, and energetic properties features of 4,5disubstituted 3,6-di-tert-butyl-o-benzoquinones. Identied contacts of the C=OH(tBu)-type (2.373.83 kcal mol-1) can be interpreted as intramolecular hydrogen bonds. These hydrogen bonds were not considered in the analysis of enthalpies of formation of the parent and t-butylated o-benzoquinones [160]. Should the literature analysis be redone? Clozapine and haloperidol are two common antipsychotic agents. With the purpose to develop compounds with the clozapine-like prole of high dopamine D4 and serotonin 5-HT2A receptor afnity for the treatment of schizophrenia Capuano et al. [161] synthesized, characterized, and determined X-ray crystal structures of three new prospective antipsychotic agents, one originating from the structural hybridization of the commercial therapeutics, clozapine, and haloperidol, while the others possess an alternative tricyclic nucleus derived from JL13, a clozapine-like atypical antipsychotic. Clozapine is a dibenzo1,4-diazepine derivative; haloperidol is a piperidine-4-ol derivative. No thermochemical data is seemingly available for 1,4-diazepines, save from a study of their basicity [162]. Piperidine-4-ols have been discussed in the context of enthalpies of formation [163, 164] and of their enzymatic interconversion with the related 4-piperidiones [165]. Gholivand et al. [166] synthesized and characterized by IR, 1H-, 13C-, 31P-NMR spectroscopy and CHN elemental analysis four new phosphoric triamides derived from isonicotinamide with the general formula 3-NC5H4C(O)NHP(O)XY (X = Y = Cl; X = Y = NHC(CH3)3; X =Y = N(C4H9)2; X = Cl, Y = N(C2H5)2. Two new polymorphs of the compound with X = Y = NHC(CH3)3 for which X-ray crystal structure were determined were obtained. These compounds form centrosymmetric dimers via intermolecular hydrogen bonds. Due to different strengths of hydrogen bonds a three-dimensional polymeric cluster is formed in the rst while two-dimensional polymeric chain is formed in the case of second compound. The enthalpies of formation of isonicotinamide and its 2- and 3-pyridinecarboxamide isomers (nicotinamide and picolinamide), and also of isonicotinamide and nicotinamide Npy-oxides have been reported [167]. Picolinamide Npy-oxide has seemingly not been studied by thermochemists. Its photochemistry shows [168] rearrangement to N-formylpyrrole2-carboxamide, a likewise thermochemically uncharacterized species. A new ruthenium arsine complex with pyrazole ligand [RuCl3(AsPh3)(C3H4N2)2]0.5CH3OH complex has been prepared and characterized by X-ray structure analysis and IR and UVVis spectroscopy by Maecki and Kruszynski [169]. Next to DFT and time-dependent DFT methods also natural bond orbital (NBO) analysis were used to calculate the electronic structure and UVVis spectrum. Good agreement between experimental and calculated UVVis

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spectra was obtained. There are three isomers RuCl3(AsPh3)(C3H4N2)2: the isomer with the two pyrazoles cis to each other and the arsine trans to one of them is the one that was studied. What is the relative energy of this species and the other two isomers in which the arsine and the two pyrazoles are all cis, and the pyrazole is cis to the two pyrazoles which are trans to each other? In the theoretical study by Chermahini et al. [170] DFT and ab initio calculation were employed to study the hydrogen bond interactions of dimer of diuoroacetic acid. Eight different conformers were considered. The calculations predict the order of stability in monomeric diuroacetic acid: EHC [ EFC [ EHT. The interaction energy of dimer of diuoroacetic acid is enough to overcome the relative stability of the monomers and dimer formation proceeds. As well understood as the hydrogen bonding in the dimer is as well as conformational preferences from this study, reliable information as to the value of the enthalpy of formation of diuoroacetic acid itself is still lacking, cf. [171, 172]. In the theoretical study by He et al. [173], periodic DFT calculation was used to investigate crystalline 2,6-diamino3,5-dinitropyridine-1-oxide, an important explosive and raw materials for preparing high energetic explosive. The insight into chemical molecular properties was obtained by analyzing band structures, densities of states and charge distributions. The theoretical lattice energy of the crystal was predicted to be -166.03 kJ mol-1. How does this lattice energy compare with this quantity for the 1,4dioxide, the unoxygenated heterocycle and the isomeric 4-oxide? In the article by Zhu and Xiao [174] recent papers on rst-principles band gap predictions of the impact sensitivity for different classes of energetic crystals were reviewed. It was shown that the rst-principles band gap criterion is applicable to different series of energetic crystals with similar structure or with similar thermal decomposition mechanism and therefore this principle could be used for molecular design of high-energy density materials. These authors discuss metal azides. We note a recent paper that discusses the anomalously high electron afnity of azido radical [175] and thus the stability of species with the azide ion such as these metal azides.

Issue 4 Issue 4 of the 2010 review begins with an editorial written by Hargittai [176] on the occasion of publishing the new book by Victor McElheny Drawing the Map of Life describing the huge importance and background of Human

Genome Project (HGP) completed in 2003 by succeeding to determine the entire DNA sequence. In the theoretical study by Wu et al. [177], DFT was used for the purpose of studying the structures and electronic properties of endohedral metallofullerenes TM@C24 and TM@C24H12 (TM = Cr, Mo, W). The results show that TM atoms bind over the pentagon ring inside the C24 cage. The analyses of dissociation energy and energy gap indicate that these compounds are not only thermodynamically, but also considerably kinetically stable. We note that the simplest species involving Cr, Mo, and W, the bis-cyclopentadienyl or ocene derivatives Cp2TM, are all known. The enthalpy of formation of the Cr species is well-established [178, 179], while that with Mo and W remain unmeasured except as oxidized (higher metal valence) form with afxed ligands [180]. In the experimental paper by Petek et al. [181], synthesis and X-ray crystal structure of o-hydroxy Schiff base derivative, (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol was synthesized and its molecular geometries at the different stages in tautomerism of (E)-2-ethoxy-6-[(2methoxyphenylimino)methyl]phenol studied. The Harmonic Oscillator Model of Aromaticity (HOMA) indices were calculated for each step of a potential energy surface (PES) scan. This showed that there is a dynamic equilibrium between the aromaticity level of the phenol and chelate ring. How do the alkoxy groups affect the aromaticity? We recall a study comparing the enthalpies of formation of the isomeric methoxy and dimethoxyphenols [182]. In the following theoretical paper, Farmanzadeh and Ashtiani [183] proposed single molecular wire, 4,40 -[ethane-1,2-diylidenedi(nitrilo)] dibenzenethiol and studied electric eld effects on the structural and electronic properties by employing DFT. The results show that the electronic structure is more sensitive than geometric structure to both directions of the applied electric eld and that with increasing the electric eld X component of electric dipole moment and total dipole moment increase continuously. We note the NC6H4S substructure of the above key species and that there are but three species containing this thioaniline functionality with a measured enthalpy of formation, phenothiazine, 1,3,7,9-tetranitrophenothiazine5-oxide and cis-5a,6,11a,12-tetrahydro[1, 4]benzothiazino [3,2-b][1, 4]-benzothiazine [184]. None of these, however, have the p-N,S substitution pattern found in the above benzenethiol derivative. Aghabozorg et al. [185] report the synthesis and characterization including X-ray crystal structures of three new metal compounds (H2bda)[Mn(pydc)2]3H2O, (H2bda)[Zn (pydc)2]3H2O, and (H2bda)3[Ce(pydc)3]24H2O (bda = butane-1,4-diamine, pydcH2 = pyridine-2,6-dicarboxylic acid). In the crystalline network hydrogen bonds, pp stacking, and ion pairing play important roles in the

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formation of supramolecular structures. The complexation studies on these compounds in addition to Ni(II), Cu(II), and Cd(II) compounds including the (H2bda)(pydc) ion pair have also been performed. What about other diamines? It is perhaps surprising that there are no thermochemical data for butane-1,4-diamine. Then again, of all the a,x-diaminoalkanes, only the ethane and hexane [186] derivatives have been so-investigated. A series of theoretical studies then follow. In the rst Wanno and Ruangpornvisuti [187] report use of DFT for studying electronic properties and structural properties of helical thiophene carbonsulfur oligomers, H2(C2S)nC2H2 (n = 120). It was found that helix of the icosamer (H2(C2S)20C2H2) makes one full turn for every approxi along its length and its inner diameter is mately 3.493 A . It may be asked how the aromaticity approximately 4.04 A varies with n. Then again, it must be asked are we using the thermochemical, magnetic, or geometric criterion for aromaticity (see [188] for a study of the n = 2 case). Mohajeri and Alipour [189] next describe use of conceptual DFT with the aim to compare the site selectivity in the complete series of dichloropyridines as ambiphilic molecules toward the reactivity and regioselectivity. Nucleophilic and electrophilic characters were analyzed. Of the six position isomers only 2,5-dichloropyridine is not a dually active molecule and is just prone to nucleophilic attack while remaining ve are ambiphilic. The enthalpy of formation of diverse chloropyridines is discussed in Refs. [190, 191]. In the following paper, Deng and Zhou [192] used DFT to study two complexes with signicant antitumor activity, [Ti(g5-C5H4{CMe2CH2CH2CH=CH2})2Cl2] and [Ti{Me2 Si( g 5 -C 5Me 4 )( g5 -C 5 H 3 {CMe 2 CH 2 CH 2 CH=CH 2})}Cl 2], which have different substituent monofunctional bindings to the purine bases and phosphate group which are potential binding targets. Results reveal that the monoaquated complex binding to guanine shows the smallest activation free-energy with 15.3 kcal mol-1 for the former and 21.5 kcal mol-1 for the latter complex. In the rst diaquated compound, the lowest activation-free energy is 16.7 kcal mol-1 for the guanine closely followed by the phosphate group by 18.3 kcal/mol, while the lowest activation-free energy is 16.9 kcal mol-1 for the second complex binding to the phosphate group. Additionally, major electronic characteristics were investigated. Are we right to assume there is but a negligible effect of the p electrons in the dimethylpentenyl substituent? Then experimental paper by Zhang et al. [193] follows in which synthesis and characterization by elemental analysis, spectroscopic methods, and X-ray crystal analysis of a series of dinuclear and trinuclear half-sandwichzirconocene complexes derived from (diphenyl-, dibenzyl-)phosphate and methylphenylphosphinic acid is

reported. The results reveal the importance of experimental conditions for the design of molecular structures. The trinuclear species contain a central l3 oxygen. How strong is the ZrO bond for these triply bridged species as opposed to the more customary doubly bridging oxygen? There are but few cases of multiply bridging oxygen for which the thermochemistry is known. Among them are the so called basic beryllium salts or beryllium oxy salts of the generic formula Be4OX6 with a l4-oxygen at its core (X = nitrate [194], acetate [195], and propionate [193]). Alkorta and Elguero [196] investigated the absolute 13C shielding of 13 methane derivatives (CH3X, X = CH3, CN, NH2, NO2, OH, F, Cl, Br, SH, SeH, PH2) and proposed a method for correction of chemical shifts obtained by DFT calculations for carbon atoms directly linked to heavy atoms that takes into account a quadratic variation with the atomic number. It is well-established that the CO bond in CH3OH is different than in (CH3)2O as shown by their different proton afnities [19]. Machura et al. [197] managed to synthesize and characterize by IR, UVVis spectroscopy, magnetic measurements, and X-ray crystallography a novel rhenium(III) complex [ReBr3(dppt)(OPPh3)] (dppt = 5,6-diphenyl-3-(2pyridyl)-1,2,4-triazine). Using DFT approach the electronic structure was determined. Spectroscopic and magnetic properties were revealed to be characteristic of mononuclear complexes with d4 low-spin octahedral Re(III) complexes (3T1g ground state). How different is the binding of 3-(2-pyridyl)-1,2,4-triazine and the isomeric 3,30 -bis(pyridazines)? Insufcient is known about the energetics of substituted pyridazines and triazines to attempt answering this about metal complexes. Systematic investigation by X-ray structural and thermal analysis of solvates of nevirapine used in combination with other antiretroviral drugs to treat HIV-1 infection and AIDS, with the homologous series of primary alcohols CH3(CH2)nOH with n = 27 is then reported by Steiger et al. [198]. Nevirapine is a tetraaza derivative of dibenzosuberane. The parent heterocycle is thermochemically uncharacterized; only recently, the enthalpy of formation of the corresponding carbocycle was reported [199]. In the paper by Kaczmarek et al. [200] synthesis and characterization by spectroscopic methods and X-ray structural analysis of (La(III), Eu(III), Gd(III), Er(III), Tm(III), and Lu(III) complexes containing N,N0 -bis(salicylidene)-4-methyl-1,3-phenylenediamine (H2L) ligand is presented formed by self-assembly formation of dinuclear lanthanide salicylaldimines. Crystal structure determination revealed a rare coordination pattern of salen-type ligand. There is a 12 kJ mol-1 spread in the enthalpies of formation of the three isomeric phenylenediamines, as solids. Now, how different are thus the related isomeric salen-type ligands or any such complexes.

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Hamza [201] report on the synthesis of 5,6,11,12-tetrahydrodibenzo[a,e]cyclooctene (THDC) and its two selectively deuterated isotopomers which were studied by resonance-enhanced two-photon ionization spectroscopy in a supersonic jet expansion. The results showed that about 90% of THDC in the gas phase exists in the twist-boat and the remaining 10% in chair conformation. The enthalpy of formation of the 5-keto species has been measured [202] but not that of the parent, three-ring compound mentioned above. We welcome that of this species and note the comparison of the enthalpies of formation of benzocycloalkanes the corresponding keto compounds is of continuing interest, e.g. [203] for a study of indane and the isomeric indanones. In the study by Kaynak et al. [204] synthesis, characterization including X-ray structural characterization and theoretical investigations of two novel derivatives of 1,2,4triazolo[3,4-b]-1,3,4-thiadiazine, 3-[2-(4-methoxyphenyl) ethyl]-6-phenyl-7H-1,2,4-triazolo-[3,4-b]-1,3,4-thiadiazine and 3-[2-(3,4,5-trimethoxyphenyl)ethyl]-6-phenyl-7H-1,2, 4-triazolo-[3,4-b]-1,3,4-thiadiazine having analgesic anti-inammatory activity is reported. The six-membered thiadiazine ring adopts the screw boat conformation in both compounds. Potential energy surface scans were drawn. We know of no thermochemical studies for thiadazines. For dithiazines, admittedly 1,3,5- and not 1,3,4-derivatives, there is none but the over 100-year-old study [205] which is simultaneously suspect and suggestive. Campanelli et al. [206] in their contribution describe advantages and limitations of gas-phase electron diffraction for determining molecular structure of ve different benzene derivatives, 1,4-diuorobenzene, 1,3,5-triuorobenzene, 1,4-dichlorobenzene, 1,3,5-trichlorobenzene, and silylbenzene. The report is rather unique, as it is only rarely possible that the analyses can be repeated independently by the same technique in two different laboratories. Except for the last species, the enthalpy of formation of each of these species is known. As such, we are thwarted from comparing the energetics of the phenyl transfer reaction 4C6 H5 EH3 ! C6 H5 4 E 3EH4 5

for E = C and Si. Ethyl 2-methyl-4-(4-methylbenzoyl)-5-(4-methylphenyl)7-oxo-3,3a-dihydropyrazolo[1,5-c]pyrimidine-3-carboxylate and ethyl 2-methyl-4-(4-methylbenzoyl)-5-(4-methylphenyl)7-thioxo-3,3a-dihydropyrazolo[1,5-c]pyrimidine-3-carboxylate are interesting because of diverse medical and biological activities of pyrimidine derivatives. These species nal were successfully synthesized and characterized by O et al. [207] by reactions of 1-amino-5-(4-methylbenzoyl)-4(4-methylphenyl)pyrimidin-2(1H)-one/-thione with ethyl acetoacetate. Theoretical calculations (DFT, NBO analysis, and Fukui function) revealed the former compound is more

stable than the latter. We note the initial synthetic step involves furan-2,3-diones. To the extent that furan is aromatic, are these species at least antiaromatic because of their nominal 4 p electrons as discussed for the isomerically related furan-2,5-dione (more commonly known as maleic anhydride) [208]? Isomerization of azobenzene derivatives is important from the perspective of their applications. Using DFT Zhu et al. [209] studied cistrans isomerization mechanisms in the S0 and T1 states of 3,30 -azobenzene disulfonate. In the S0 state the energy barrier is 22.79 kcal mol-1 and it concerns mainly the rotational pathway around the NN double bond while the energy barrier of T1 state is 5.02 kcal mol-1 and requires a change in spin-multiplicity. The strength of NN bonds in azo compounds shows considerable dependence on the afxed groups [210]. How is that reected in the rotational barriers of these azo compounds? Picolinic acid derivatives form a group of bidentate ligands effectively complex the tricarbonyltechnetium(I) and rhenium(I) cations and form promising radiopharmaceutical precursors. Using DFT, Fuks et al. [211] proved that in vitro behavior of tricarbonylrhenium(I) and tricarbonyltechnetium(I) complexed by the N-methyl-2pyridinecarboxyamide and chloride, water or tert-butyl-3isocyanopropionate is thermodynamically controlled. The energy of formation of the complexes containing tertbutyl-3-isocyanopropanoate ligand is more negative by a few kcal mol-1 than energy of those having a coordinated water molecules instead. The energetics of p-complexes of the valence isoelectronic tricarbonylmanganese(I) cation has recently been reviewed [212]. Comparison with the above technetium and rhenium species is welcomed. Hayvali et al. [213] report the synthesis and characterization of the substituted benzyloxybenzaldehyde derivatives by reaction of the appropriate hydroxy benzaldehydes with p-nitrobenzyl bromide in DMF and NaOH. After 5 h of reux with furfuryl amine the corresponding imine compounds were formed, and the crystal structures were determined. After longer reux time, cyclization reaction with a CO bond occurs and corresponding benzofuran derivatives are formed. Quoting a recent review [214], de-benzoannnelation resulting in an aromatic one-ring species (e.g., benzofuran) is generally more favorable than processes involving non- or antiaromatic species. This was discussed in context of heterocyclic analogs of indene and indane, cyclopentadiene and cyclopentene, with benzoannelated 5-membered rings. What about other size rings, e.g., the 6-membered ring containing analogs of naphthalene and its hydrogenated derivatives? A series of theoretical papers then follows. Using DFT, Zhu and Xiao [215] studied substituent effects on the electronic structure and properties of the 1H-tetrazole crystal and variously substituted derivatives. The

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calculated thermodynamic properties show that the order of their thermodynamic stability is 5-amino-1H-tetrazole \ 5-methyl-1H-tetrazole \ 5-azido-1H-tetrazole \ 1H-tetrazole and that their decomposition reactions are favorable at high temperature. An attempt to correlate the impact sensitivity of the four crystals with their band gaps showed that the rst-principles band gap criterion can be used to predict impact sensitivity for the substituted 1H-tetrazoles. Do the same substituent trends for stability apply to the isomeric triazoles, diazoles and parent pyrroles? In the subsequent paper by Huang et al. [216] use of DFT, the QTAIM and NBO analyses to study hydrogen bonds and the interaction characteristics in cysteinepropanoic acid complexes are reported. More than 10 kinds of H-bonds including intra- and intermolecular H-bonds have been found. The results show that the important factors for the stability of complexes are strength of H-bonds and the deformations. What about alanine and serinepropanoic acid complexes? When can we ignore hydrogen bonding involving SH groups? Further Huang et al. [217] report use of DFT, QTAIM, and NBO to study geometries, energies, and IR characteristics of the intermolecular hydrogen bonds in complexes formed between N-protonated adrenaline and dimethyl sulfoxide. While the H-bonds involving amino or hydroxyls as H-donor are dominant in complexes and considered as strong H-bonds, weak H-bonds, such as p H-bonds and H-bonds involving methyl or methenyls (C2H6 and C5H7 of AdH?) as H-acceptors were found in complexes as well. The reader will note we said N-protonated earlier in this paragraph. Was there a choice? For a discussion of the alternative N and O protonation sites in aminoalcohols, the reader is referred to Ref. [218]. Using DFT the structures and properties of the planar double hydrogen-bonded imidazoleadenineimidazole trimer were studied by Cui et al. [219]. The H-bond generated by NH group of adenine decreases signicantly in length upon oxidation to form the radical cation and signicant IR spectra red-shift occurs upon oxidation for all NHH bonds. The molecular orbital analysis was effective to reveal the geometry variations and the IR spectral shifts. We note that while the ionization energy of imidazole is greater than that of purine as the authors point out, the proton afnities are in the reverse order [19]. The theoretical study by Qi et al. [220] follows with a study of the insertions of the p-complex silylenoid H2SiLiF into CX bonds of CH3XHn-1 (X = F, Cl, Br, O, N; n = 1, 1, 1, 2, 3) using DFT is the following. The results revealed that substituted silanes H2Si(XHn-1)CH3 and LiF are formed. The reaction barriers for the insertion of the p-complex into CX bond increase for the same-row element X from right to left in the periodic table and do not change much for the insertion of the same family element

X. All this is sensible except that we also note there are no reliable measurements of the CF bond strength in CH3F or equivalently, of the enthalpy of formation of methyl uoride. Alkorta and Elguero [221] report conformational analysis of medium-sized rings, namely four derivatives of cyclooctadiene bearing two aromatic or heteroaromatic rings. Good agreement between experimental results and theoretical results was reached. We look forward to studies comparing the ndings of Hamza [201] to this article. In the last paper in this issue Zhan and Feng [222] report on synthesis of two 3D supramolecular complexes constructed from p-thioacetatebenzoic acid (H2L), [Mn(HL)2 (bpp)2(H2O)2]n and [NiL(4,40 bipy)(H2O)3]nnH2O (bpp = 1,3-bi(4-pyridyl)propane, 4,40 -bipy = 4,40 -bipyridine). The former compound exhibits intense structure-related uorescent emission bands. The latter exhibits irreversible redox processes. The enthalpy of formation of numerous substituted benzoic acids has been studied. We know of no examples where the substituent is bonded to the benzene ring by a sulfurhowever, enthalpy of hydrolysis studies discussing CH3C(O)O- and CH3C(O)S-substituted benzoic acids is recalled [223, 224].

Issue 5 Issue 5 of the present volume opens with the editorial by Hargittai [225] written in honor of Gyorgy Kepes, designer and art theorist. Although not a chemist Kepes managed to inuence chemistry and science with his visionary approach in design and so ultimately accomplishing design in science. The next paper is a theoretical study by Beheshtian et al. [226] in which the DFT approach was used to study the interaction of water with the outer layer of single-walled boron nitride nanotubes. The results suggest that water can be adsorbed on the surface through BO interactions by a signicant charge transfer and NHO hydrogen bond interactions, and that the water is better adsorbed as the cluster size increases. As an archetypical study, we ask what is the interaction energy of borazine with water and is B or N-bonding to water preferable? What is the hydration energy of borazine to form the saturated B,B0 ,B00 -trihydroxyborazane? We note that borazine photochemically reacts with water to form the B-hydroxy derivative and the corresponding ether [227], the latter being shown to be more stable. By contrast, for the isoelectronic benzene derivatives, phenol is rather much more stable than the corresponding ether (?water). In multiple types of non-bonded interactions it is intuitively expected that they would be formed hierarchically based on energetic gains. In the paper by Rathore et al.

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[228], synthesis of derivatives of 3-azabicyclo[3.3.1] nonan-9-one, namely 10,12-bis(2-uorophenyl)-11-azatricyclo[7.3.1.02,7]trideca-2,4,6-trien-13-one, and its bis(2methylphenyl) and bis(2-methoxyphenyl) counterparts, is reported and the interactions studied. Preferences for weaker interactions over strong hydrogen bonds were observed. How strong are the nitrogencarbonyl transannular interactions in these species and how are these interactions impacted by the above substitution of the two phenyl groups? What follows is a theoretical study by Goodarzi et al. [229], who investigated energies of the gas phase reaction of Se with O3 using DFT. As calculationally shown, SeO3(D3h) and (SeO ? 3O2) products are obtained via transformations of the linear chain SeO3 isomer. Both reactions are at atmospheric pressure and temperature of 298.15 K exothermic and exergonic (DH \ 0, DG \ 0). We note SeO2 is a classic oxidizing agent in organic chemistry; presumably SeO3 would be even more oxidizing. Sulfur dioxide is an occasional reductant. This is reected in some 70 kJ mol-1 difference in the enthalpies of formation of selenium dioxide, as solid, and sulfur dioxide, as gas (where the solid is unequivocally even more stable by an unstated enthalpy of sublimation). The difference is over 200 kJ mol-1 for the trioxides for the same choice of phases. Why do the dioxides and trioxides differ by so much? He et al. [230] in their experimental paper report on synthesis and characterization including X-ray single crystal analysis of 3d4f heterometallic coordination polymers based on 2,5- and 2,6-pyridinedicarboxylic acid, [Cu3Eu2 (2,5-pydc)6(H2O)12]4(H2O), [Zn2Eu2(2,5-pydc)5(H2O)2] 3(H2O), and [Co3Ln2(2,6-pydc)6 (H2O)6]4(H2O) (Ln = Eu, 3; Dy, 4) (H2pydc = pyridinedicarboxylic acid) under hydrothermal conditions. The results, which indicate that compounds generate 3D heterometallic coordination frameworks containing 1D channels that are occupied by lattice water guest mole, are important from the perspective of further construction of novel 3D lanthanidetransition metal heterometallic coordination frameworks. We note the transition metal is always divalent while the lanthanide is always trivalent. Some transition metals are naturally trivalent while some lanthanides enjoy the divalent oxidation state. Can related species be prepared with these reversed oxidation states and how does that effect the structure, and thereby properties, of these complexes? With the aim to investigate inuence of oxidation damage on the guanine:cytosine base pairs Qiu et al. [231] studied structures of their derivatives with MllerPlesset perturbation theory. Marked differences in the interaction energy were shown: among the hydrogen bond complexes ranging from -24.1 to -13.0 kcal mol-1 for derivatives of the guanine bonded to cytosine derivatives and from -24.5 to -9.7 kcal mol-1 for cytosine bonded to guanine

derivatives. Thermochemical data for the free component nucleobases and their derivatives are almost totally absent in the experimental literature (see Domalski [46] but not Pedley). We note that the unmodied cytosine and guanine among the few cases where enthalpies are available for both the solid and the gas phase species. With the purpose of investigating the role of the Csp3H/p and Csp2H/p interactions on the interactions on the conformational stability of molecules Hamza [232] synthesized 2-methylindane and 2-phenylindane. By using resonantenhanced two-photon ionization spectroscopy in combination with ab initio calculations axial and equatorial conformers of 2-methylindane were observed while only the axial conformer was observed for 2-phenylindane in the supersonic jet expansion. Intramolecular CH/p interactions are more important in determining the conformational stability of 2-phenylindane than 2-methylindane, which was ascribed to the higher acidity of the Csp2H bond than that of Csp3H bond. How do these intramolecular interactions affect the molecular stabilityin the particular, how exothermic is the following reaction 2-methylindane phenylcyclopentane ! 2-phenylindane methylcyclopentane 6

Using ab initio methods Bhattacharyya et al. [233] studied structures, stabilities, and dissociation of RSiN (R = H2B, H2N, H2P) which were shown to be more stable than their corresponding RNSi isomers. The conversion of H2BNSi to H2BSiN was found to be more facile than in the other systems. Among isomers, only the H2BSiNH2BNSi pair are both linear. The dipole moment of H2NSiN is the largest and that of H2NNSi is the smallest among all the isomers. A comparison of these ndings with the corresponding RGeN and RNGe, and the corresponding phosphorus-containing, species is welcomed. For none of these species is the enthalpy of formation, or even of isomerization, known from experiment. miechowska et al. [234] an optimized In the work by S procedure for conversion of natural isothiocyanates to N-(1-methylbenzimidazolyl)-N0 -allylthiourea, N-(1-methylbenzimidazolyl)-N0 -benzylthiourea and N-(1-methylbenzimidazolyl)-N00 -phenethylthiourea is presented. The obtained products were characterized spectroscopically and their X-ray single crystal structures were determined. Using DFT, the possible explanation for the existence of three tautomeric forms of the synthesized compounds in solution was offered. The thermochemistry of isothiocyanates is disappointingly sparse. While the enthalpy of formation of methyl isothiocyanate is archived in Pedley with a presumably trusted value from a rather contemporary primary reference [235], that for the phenyl derivative is not so found and the ignored primary source for this information is over 100 years of age [236].

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Experimental structural data considering the chemical and biological importance of conformations of dimers and pentamer (fondaparinux) of the glycosaminoglycan heparin, and their ionized forms are rare and currently it is experimentally difcult or even impossible to obtain the desired data. In the theoretical study by Remko et al. [237] geometries and energies of the aforementioned compounds were investigated using DFT. As shown calculationally the most stable neutral structures are stabilized by hydrogen bonds while equilibrium structure changes upon dissociation are signicant. Heparin is a derivative of the rather exotic 6-carbon sugar, the monosaccharide idose. Computational comparison of the energetics of idose with that of other hexoses has been reported in Ref. [238, 239]. No experimental data for idose or any idose derivative is seemingly known. In the experimental study by Zhao et al. [240], synthesis and characterization including X-ray single crystal structures of Schiff base ligand 4-phenyl-1-(4-methoxyl1-phenylethylidene)thiosemicarbazide (HL) and its chelate complexes, ZnL2, NiL2, and CuL2 are reported. While so complexed Zn(II) ion adopts a distorted tetrahedral geometry, Ni2? and Cu2? ions adopt distorted square planar congurations. DFT calculations are in line with the results of UVVis spectral investigations. Aliphatic thiosemicarbazones have been studied calorimetrically; their aromatic counterparts such as the above HL species have not. With the aim to investigate optical and non-linearoptical properties, Ivanova and Spiteller [241] synthesized four novel organic salts of mandelic acid, pyridinium-4aldoxime mandelate, 1-aminoisoquinolinium mandelate mandelic acid, 2-amino-8-hydroxyquinolinium mandelate, and phenylalaninamide mandelate monohydrate. Compounds were characterized and their X-ray single crystal structures determined. The optical and non-linear-optical properties were predicted also by applying ab initio and DFT methods. We recognize mandelic acid as a-hydroxyphenylacetic acid and note its enthalpy of formation has been determined. That of the redox related a-ketophenylacetic acid [242] and the deoxygenated phenylacetic acid [243, 244] have also been so studied. Few sets of RCH(OH)COOH, RC(O)COOH, and RCH2COOH are available for thermochemical comparison, namely the above R = phenyl, methyl, and carboxymethyl. In the experimental paper by Khalaji et al. [245], synthesis, characterization, and X-ray single crystal structures of (E)-2-(2,4-dimethoxybenzylidene)thiosemicarbazone and of (E)-2-(2,5-dimethoxybenzylidene)thiosemicarbazone are reported. The compounds were also studied by using ab initio and DFT methods. It would be interesting to compare the enthalpy of formation of these two species with those of 2,4-dimethoxybenzoic acid and that recently found for its 2,5-isomer [246].

Synthesis, characterization, and X-ray single crystal structure determination of (Z)-3-(3-oxobenzo[b]thiophen2(3H)-ylidene)indolin-2-one (thioindirubin) is described in the next paper by Shishkin et al. [247]. Formation of intramolecular CHO and SO interactions has been shown for in this compound and the result conrmed by AIM and NBO analyses. The aforementioned compound is related to benzo[b]thiophene as indigo is to indole. As such, the enthalpy of formation of thioindirubin is thus asked for, noting that the enthalpy of formation of indigo has been measured [248], albeit some 120 years ago. We note that the latter quantity was discussed in a recent study of the energetics of C=C bond cleavage for a variety of olens [249] and so redetermination of this value is welcomed as well. In the study by Ronova and Bruma [250], literature data on the glass transition temperature of various polyimides were considered and related to their calculated conformational parameters for the purpose to investigate in what way the glass transitions temperatures are inuenced by the rigidity of either diamine or dianhydride component. In this respect also the solubility of different polyimides was discussed. Many of these polyimides contain nominally aromatic or antiaromatic multiple ring species. Now, are they aromatic or antiaromatic? The reader is addressed to thermochemical studies as the enthalpies of formation of derivatives of maleimide [207], phthalimide [207], 1,8-naphthalimide [251], and 1,2,4,5-benzenetetracarboxylic acid diimide [252]. As proven by X-ray single crystal structure determination, molecule of ZnCl2(BzTz)2 ([BzTz = N-(5,6-dihydro4H-1,3-thiazin-2-yl)-2-aminobenzimidazole] exhibits positional disorder in three of its atoms. In the paper by ndez et al. [253] its structure was determined by a Mele charge ipping algorithm. The results were compared with the results as obtained by direct methods and showed the effectiveness of charge ipping algorithm in the cases of positional disorders. The S in the thiazine ring can be exchanged with the N in either the amino group or the imidazole. What is the difference of the enthalpy of formation of these various isomers? There are no dihydro-1,3thiazine derivatives in the literature with measured enthalpies of formation to immediately guide us; thioimidates, their acyclic counterparts are likewise scarcely known to the thermochemistry community, cf. the methylation studies of Beak et al. [254, 255]. In the experimental paper by Alpaslan et al. [256], synthesis, characterization, and X-ray single crystal structure determination of (E)-2-(1-(2-(4-methylphenylsulfonamido)-ethyliminio)ethyl) phenolate is reported. The results have shown that the compound exists in the zwitterionic form, which is stabilized by the intramolecular N?HO hydrogen bond. The structure of the compound was

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reproduced also by theoretical DFT and HF (HartreeFock) methods which also revealed that the OH form of the compound is more stable than NH form. Speaking of charged forms, the gas phase acidity of 4-methylbenzenesulfonamide has been measured [257]; the corresponding gas phase basicity for this or any other has not. As shown in the theoretical study using DFT by Dobosz et al. [258] enaminone is the most stable form among tautomeric forms of 8-acyl-2-(quinolin-2-yl)-1,3-diketones. Bifurcated hydrogen bonds appear in the 8-acetyl derivatives. There are few enaminones for which there are enthalpies of formation data. The aforementioned indigo is among them [247]. Cannot we do better than this multifunctionalized species from the early days of calorimetry for our contemporary thermochemical comparisons? Synthesis, characterization, and X-ray single crystal structure determination of two new compounds of 3,5-diaryl-1H-pyrazoles, interesting from the perspective of their biological properties is then reported by Zheng et al. [259]. As revealed, in both compounds, 3(5)-(4-tertbutylphenyl)5(3)-(naphthalene-2-yl)-1H-pyrazole and 5-(4-(benzyloxy) phenyl)-3-(furan-2-yl)-1H-pyrazole, intermolecular hydrogen bonds interactions lead to the formation of dimers with 4 R2 2(6) and R4(10) motifs. Systematics of the sublimation enthalpy of diarylpyrazoles have been studied [260]; no such study of their enthalpies of formation is apparent. With the explicit purpose to provide better understanding between structure and energy of nitro compounds, tke and Liebman [39] compared the enthalpies of Klapo formation of corresponding species with trinitromethyl and trimethylmethyl (t-butyl) groups. That more thermochemical studies on these species are desired is obvious from the analyses during which surprisingly few corresponding pairs for which the data were available were found in the literature. The span for those found was over a 150 kJ mol-1 range. In the theoretical by Enchev and Angelova [261], the tautomerism of oxadiazole, thiadiazole, and selenadiazole containing hydroxy, mercapto, or selenyl groups in positions 2 and 5 of the ve-membered ring was investigated. The results indicate that if the exocyclic group is a mercapto or selenyl group, the most stable tautomer is the mixed mercapto/thione or selenyl/selone form. These species have RC(X)YR0 groups where X and Y = O, S, and Se. The energetics of the simple esters, the methyl dichalcogenoacetates (R = R0 = CH3) has recently been theoretically investigated [262], experimental data being almost totally absent for these species. For both classes of molecules, heterocycles and esters alike, extension to tellurium-containing species is welcomed. With the purpose to study the triple hydrogen bonds, which are expected to strengthen the association especially with the peruoroalkyl derivatives, interactions between

2,6-bis(alkylcarbonylamino)pyridines with succin- and maleimide and with 2,20 -dipyridylamine were investigated in miaowski et al. [263] using NMR the following paper by Os and DFT approach. In addition, also X-ray single crystal structures of 2,6-bis(triuoromethylcarbonylamino)pyridine and 2,6-bis(pentauoroethylcarbonylamino)pyridine have been determined. Good agreement between experimental observations and theoretical calculations was observed. We recognize these two species as amides of triuoroacetic and pentauoropropionic acid. The difference of the enthalpy of formation of any such amides, or even the parent acids, remains unknown. That for the corresponding methyl esters is 443 kJ mol-1, where the data for the former species is taken from the reaction calorimetry of Guthrie [264]. Is this difference reasonable? For comparison, the difference is 439 kJ mol-1 for hexauoroethane and octauoropropane wherein the COOH group has been exchanged for CF3, and 420 kJ mol-1 for 2,2,2-triuoroethanol and 2,2,3,3,3-pentauoropropanol wherein the COOCH3 group has been exchanged for CH2OH. Using DFT, Mohajeri and Davari [265] studied 15 complexes, more precisely, stacked pairs of the ve nucleic acid bases, A, G, C, T, and U. The bond delocalization and aromaticity of isolated bases have been compared to those for their counterpart in the stacked pairs. It is concluded that stacking interaction reduces the aromatic character of the nucleic acid base fragments and that the variation in the aromaticity of imidazole ring was found to be less than pyrimidine ring. We ask the simple question about additivity: how close is the stacking energy in the B1B2 stacked pair to the average of those of (B1)2 and (B2)2? A quick look shows that there is no simple relation. And so we are thwarted in nding trends in oligonucleotides, much less in natural nucleic acids. Gruber et al. [266] managed to synthesize and determine X-ray single crystal structures of solvated crystals obtained upon crystallization from dimethyl sulfoxide of constitutionally isomeric 9,10-anthraquinone-1-carboxylic acid and 9,10-anthraquinone-2-carboxylic acid. The basic supramolecular entities in the solvated crystals were shown to be OHO bonded 1:1 carboxylic acidDMSO aggregates. It is entirely plausible that the 1-carboxylic acid is less stable than its 2-isomer much as naphthalene-1-carboxylic acid is some 8 kJ mol-1 less stable than its 2-isomer [267]. Now, what are the relative stabilities of the 1-, 2-, and 9-carboxylic acids of anthracene [268]: only the enthalpy of the last and presumably most sterically hindered species is the value known from experiment [269]. Synthesis, characterization, and X-ray single crystal structure determination of a new 3D Cd(II) coordination polymer, [Cd(PMP)2]n (PMP = 1-phenyl-3-methyl-5-pyrazolone) is reported in the experimental paper by Xu et al. [270]. Each Cd(II) is four-coordinated with a distorted

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tetrahedral geometry and linked by four PMP molecules that act as bidentate bridging ligands. The synthesized compound acts as potential photoactive material with high thermal stability. What is the relative stability compared to PMP for the isomer wherein the phenyl and methyl group have been exchanged? et al. [271] synthesis In the experimental study by Repicka of ve new monomeric 3-, 4-, and 5- methylsalicylatocopper(II), and 4- and 5-methoxysalicylatocopper(II) complexes with N,N-diethylnicotinamide as monodentate terminal ligand is reported. All these compounds seem to possess octahedral copper(II) stereochemistry. The molecules are linked to supramolecular chains through hydrogen bonds, which can exist in two alternative congurations. The compound with 3-methylsalicylate anion exists in both conguration forms and is an example of conformation polymorphism. Although salicylic acid is a classical species of interest to thermochemists, the only ring-substituted derivative for which its enthalpy of formation has been measured is the diiodo compound [272] wherein the two iodines were suggested to be o- and p- to the hydroxyl group [273]. lu and Yurdakul [274] used DFT approach to Badog study geometrical and electronic properties of methylated pyridines. The small variations in the aromaticity indices have been observe which have been considered as the weak inuence on the p-electron delocalization by the substituents attached to pyridine ring. The enthalpy of formation of all three monomethyl and six dimethylpyridines are known; only that of the 2,4,6-isomer of trimethylpyridine is there such data [275]. No tetramethylpyridine or pentamethylpyridine has been so thermochemically studied. In the next theoretical paper, Bao et al. [276] investigated by DFT the hydrogen storage property of Ti containing organometallic complexes grafted on silsesquioxanes of the structure TiRH7Si8O12 (R = C4H3, C5H4, C6H5). The results of this study showed that 3d transition metal grafted silsesquioxane complexes can be used as hydrogen storage material. The average binding energy of H2 was calculated to be found to be between 0.21.0 eV. These species are recognizable as titanium half-sandwich and sandwich species for which enthalpies of formation and reaction are generally unknown save the compounds C5H5TiCl3 and (C5H5)2TiCl2 [277] and some derivatives, respectively. The following is the review article by Hofmann et al. [278]. The current investigations on the molecular mechanisms of proteins of the Structural Chemistry Program at Grifth Universitys Eskitis Institute are presented as well as future objectives. The last study in this issue is a review article by Ponikvar-Svet and Liebman [10] relating thermochemistry to the content of the articles contained in Structural Chemistry for the year 2009. As such, this paper is a conceptual ancestor of the current study.

Issue 6 Issue 6 opens with a review by Hargittai [279] discussing the 2010 Nobel Prize in Physics awarded to Andre Geim and Konstantin Novoselov for groundbreaking experiments regarding the two-dimensional material graphene. The next paper is a review by Dinadayalane and Leszczynski [280] in which diversity of the structures and salient properties of carbon nanostructures with unique diversity of carboncarbon bonds such as fullerenes, carbon nanotubes, and graphene are reviewed. The enthalpy of formation of fullerenes has been reviewed [281] that of carbon nanotubes recently measured [282]. We may say that the thermochemistry of graphene has been simulated. The enthalpy of sublimation of graphite has been estimated [283] mimicking the destacking of graphite to form graphene. The enthalpies of formation and of sublimation of a small piece of graphene, coronene [284], have also been directly studied. Two theoretical papers then follow. The rst is study by Saloni et al. [285] where investigations on structural and vibrational properties of monomertemplate systems are presented. The studies on the complex between 2,6-dinitrotoluene and methacrylic acid applying DFT and MP2 calculations were performed. Complex formation was indicated by signicant intensity of the OH stretching at *3400 cm-1 (theoretical) and *3000 cm-1 (experimental). The experimentally measured enthalpy of formation of acrylic acid has been looked at closely and found to be problematic: a new value has recently been suggested [134]. What can/should be said about methacrylic acid [286, 287]? The next paper on the hyaluronan investigations is by ny and Kova cs [288] in which conformational propPoga erties of small oligosaccharides from hyaluronan and the built-up process were studied using DFT. The sodium salt and acid have been modeled. Some new thermochemical analysis is in progress [289]. Further, Zhan et al. [290] report on the synthesis by hydrothermal reaction of 3D supramolecules synthesized from p-thioacetatebenzoic acid (H2L) and a combination of N-donor ligand of 4,40 -bipyridine (4,40 -bipy) with metal(II) ions with general formula [M(HL)2(4,40 -bipy)2(H2O)2]H2O, M = Co(II), Zn(II) and Ni(II), which were characterized by as shown by X-ray single crystal analysis the complexes are isostructural. As shown by cyclic voltammetry the electron transfer reactions in the electrode reactions of Co(II) and Ni(II) complexes are irreversible. The Zn(II) complex exhibits green uorescent emission bands at room temperature. In principle, both the benzoic and the acetic acid oxygens can be anionic and so coordinate to the metals. What are the energy differences of these isomeric complexes: how much more favored is the latter?

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SQ109 (N-geranyl-N0 -(2-adamantyl)ethane-1,2-diamine) is an ethambutol cage diamine derivative and possesses excellent activity against multi-drug-resistant (MDR) strains of tuberculosis. Onajole et al. [291] report in their paper NMR elucidation of SQ109 and ve new analogues, which have a potential activity against tuberculosis. Twodimensional NMR techniques assisted in resolving a series of overlapping signals from the methine and methylene groups. The 1-nitro and 1-ol derivatives of adamantane are both 12 kJ mol-1 more stable than their 2-isomers; 1-methyladamantane is some 16 kJ mol-1 more stable than its 2-isomer. What is the enthalpy of formation difference of SQ109 form its 1-adamantyl isomer? And how different are their bioactivities? In the Paradigms and Paradoxes column Varga and Hargittai [292] report on the use of DFT approach to compare molecular structures of basic dimers of hyaluronan and chondroitin which differ in orientation of one hydroxyl group. This information is required to provide better understanding of the functions of these biopolymers. The lowest energy structure of the former is about 20 kJ mol-1 lower than of the latter but the interconversion is hindered by high energy barrier of about 300350 kJ mol-1. Some new thermochemical analysis is in progress [288]. In the review paper by Wang [293] use of DFT study, Raman and absorption peaks of Zn3S3, Zn4S4, (Zn3S3)2, and (Zn3S3)3 clusters are presented, all species having similar units with experimental ZnS nanocrystals. Calculated Raman spectra show that the swing of ZnS appears in range of 260310 cm-1, which is in agreement with experimental results. The size of the clusters is much smaller than of ZnS nanocrystals and the observed absorption spectra of these clusters are blue-shift. There are two crystal forms of ZnS, wurzite and sphalerite: the latter is more stable by some 13 kJ mol-1. How is that energy difference reected in clusters and nanocrystals of ZnS? Further, Gu et al. [294] studied structure and aromaticity of nitrogen-containing thiocarbons and a many of them were predicted to be stable species. NICS values and magnetic susceptibility were used to estimate the degree of aromaticity of these species. As revealed the values 1 A above the molecular plane indicate the species to be nonaromatic or to have but a small degree of aromaticity. All the species studied were of the type (CS)2 n and nitrogen analogs wherein nitrogen replaces carbon. The enthalpy of formation of the simplest nitrogen-containing thiocarbon anion, (NCS)-, can be derived from the enthalpy of formation of HNCS found in Wagman and the measured gas phase acidity of this species [295]. How does this value compare with that calculated using the same protocol as in Ref. [293]? N-Alkoxy-polynitroaniline derivatives are known as compounds with interesting physico-chemical properties

such as acidity, paramagnetism, and ionophore characteristics. In the experimental paper by Tudose et al. [296] synthesis of N-alkoxy-3,5-dinitro-4-aminobenzoic acid esters (alkoxy = methoxy, carboxymethoxy, triphenylmethoxy, or corresponding amides) is presented. The compounds were characterized and their properties studied. There are surprisingly few compounds with the general formula RNHOR0 with measured enthalpies of formation [138], and very few of these compounds have R equalling some aryl group. A series of theoretical studies then follows. In the rst Zhao et al. [297] established good linear correlation between the ratio of the weakest bond dissociation energy to the total energy and the explosive impact sensitivity was found for two series of triazole energetic explosives, 1,2,3triazoles and 1,2,4-triazoles using DFT. The enthalpy of formation of 1,2,4-triazole is well established that of its 1,2,3-isomer remains unmeasured altogether. As shown in the next paper by Golmohammadi and Dashtbozorgi [298] articial neural networks were successfully employed to develop a quantitative structure property relationship model in which gas-to-wet butyl acetate partition coefcients of organic compounds were successfully predicted. How well do these partition coefcients relate to phase change enthalpies, cf. the newly developed, highly powerful correlation-gas chromatography methodology to obtain enthalpies of vaporization [299]. The geometries and the electronic structures of oligomers based on furo[3,4-b]pyridine-type heterocyclics (from monomer up to tetramer) and polymers were studied by using DFT by Ou et al. [300]. The results suggest that all these compounds have a coplanar conformation. The HOMOLUMO energy gap mainly depends on the degree of polymerization degree in the order: monomer [ dimer [ trimer [ tetramer [ octamer [ polymer. Consider now the furo[3,2-b]pyridine isomeric forms of these species and in particular its 2-amino-3-carboxamide derivative. Thermodynamic and structural studies of its complexes with manganese(II), cobalt(II), nickel(II) and copper(II) have been reported [301]. In the last of the theoretical papers in this series Ding et al. [302] performed a series of quantum chemical computations to better understand geometries, excited state spectra, energy band structures, and adsorption stability of thienyl-functionalized oligo-/polysilanes onto Au (111) surfaces. The results of the study among other results show also that the bulky supermolecular polysilanes would allow formation by the self-assembly of the thienyl-functionalized oligosilanes on Au (111) surfaces. The enthalpy of formation of numerous alkanes has long been known. The data on polysilanes is much more limited: for an experimental study of the enthalpies of formation of linear polysilanes through but the four-silicon case, see [303].

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Struct Chem (2011) 22:717740 9. Ponikvar-Svet M, Keating LR, Dodson BJ, Liebman JF (2009) Struct Chem 20:719 10. Ponikvar-Svet M, Liebman JF (2009) Struct Chem 21:1131 11. Wagman DD, Evans WH, Parker VB, Schumm RH, Halow I, Bailey SM, Churney KL, Nuttall RL (1982) The NBS tables of chemical thermodynamic properties: selected values for inorganic and C1 and C2 organic substances in SI units. J Phys Chem Ref Data 11(Suppl 2):1 12. Pedley JB (1994) Thermochemical data and structures of organic compounds, vol 1. TRC Data Series, College Station 13. Hargittai I (2010) Struct Chem 21:1 14. Xu CX, Chen LZ (2010) Struct Chem 21:9 15. Brede O, Mehnert R, Naumann W (1980) Berich Bunsen Gesell 84:666 16. Kurz D, Hennig H, Reinhold J (2001) Zeit Anorg Allgem Chem 627:1895 17. Liu Y, Liu Y, Drew MGB (2010) Struct Chem 21:21 18. Chapkanov AG (2010) Struct Chem 21:29 19. Hunter EPL, Lias SG (1998) J Phys Chem Ref Data 17:413 20. Lee JH, Ihee H (2010) Struct Chem 21:37 21. Stem MR, Ellzey ML (2010) Struct Chem 21:43 22. Piacente V, Foglia S, Scardala P (1991) J Alloy Compd 177:17 lu N, Ustabas leymanog 23. Su R, Alpaslan YB, C oruh U, Karakus S, Rollas S (2010) Struct Chem 21:59 EA, Dojc inovic -Vujas kovic SV, Sakac MN, Jovin 24. Djurendic VV, Bogdanovic GM, Klisuric OR, Stankovic SM, ED, Kojic i KM (2010) Struct Chem 21:67 Lazar DV, Fabian L, Penov-Gas 25. Zhang SS, Yin XH, Hu FL, Zhuang Y (2010) Struct Chem 21:79 26. Beak P (1977) Acc Chem Res 10:186 27. Maquestiau A, Van Haverbeke Y, Flammang-Barbieux M, Willame M (1976) Bull Soc Chim Belg 85:579 28. Hosmane RS (1984) Liebigs Ann Chem 831 29. Kruszynski R (2010) Struct Chem 21:87 30. Czakis-Sulikowska D, Malinowska A, Markiewicz M (2003) Pol J Chem 77:1363 31. Jenkins HDB, Glasser L, Liebman JF (2010) J Chem Eng Data 55:4369 32. Qiu Z, Xia Y, Wang H, Diao K (2010) Struct Chem 21:99 33. Tomura M, Yamashita Y (2010) Struct Chem 21:107 34. Miao S, Schleyer PV, Wu JI, Hardcastle KI, Bunz UHV (2007) Org Lett 9:1073 35. Zelaya CA, Stevens ED, Dowd MK (2010) Struct Chem 21:113 36. Qi Y, Mu Z, Feng D (2010) Struct Chem 21:123 37. Trzesowska-Kruszynska A (2010) Struct Chem 21:131 bel M, Klapo tke TM, Murray JS, Politzer P 38. Macaveiu L, Go (2010) Struct Chem 21:139 tke TM, Liebman JF (2010) Struct Chem 21:1051 39. Klapo 40. Ghosh T, Mukhopadhyay A, Dargaiah KSC, Pal S (2010) Struct Chem 21:147 41. Khalaji AD, Chermahini AN, Fejfarova K, Dusek M (2010) Struct Chem 21:153 42. An L, Zhou J, Zhao L, Lv Y (2010) Struct Chem 21:159 43. Ye HM, Ren N, Zhang JJ, Sun SJ, Wang JF (2010) Struct Chem 21:165 44. Maecka M (2010) Struct Chem 21:175 nen E, Valkonen A, Lahtinen M, 45. Ahonen K, Behera B, Sieva Tolonen M, Kauppinen R, Kolehmainen E (2010) Struct Chem 21:185 46. Domalski ES (1972) J Phys Chem Ref Data 1:221 rez-Garc a F, Alvarado-Rodr guez JG, Gala n-Vidal CA, Pa ez47. Pe ndez ME, Andrade-Lo pez N, Moreno-Esparza R (2010) Herna Struct Chem 21:191 48. Liu G, Yang Y, Zhang W (2010) Struct Chem 21:197 49. Glukhovtsev MN, Szulejko JE, McMahon TB, Gauld JE, Scott AP, Smith BJ, Pross A, Radom LJ (1994) J Phys Chem 98:13099

Karabyk et al. [304] studied spectroscopic properties and molecular and X-ray single crystal structure of 4-(2tert-butyl-4-methylphenoxy)phthalonitrile. A mesomeric effect between the electron-withdrawing N atoms of nitrile substituents in meta and para positions and the electron donating O atom was identied, which should be, as revealed by QTAIM slightly stronger in para than in meta position. We know of no thermochemical study of the energetics of benzenedinitriles with an appended alkoxy or aryloxy group, or any other electron-donating substituent. However, for a calorimetric study of the enthalpy of formation of the three hydroxybenzonitriles, see [305]. DFT showed in the theoretical study by Dobosz et al. [306] that (1Z,3Z)-3-hydroxy-4-(pyridin-2-yl)-1-(quinolin2(1H)-ylidene)but-3-en-2-one and (1Z,3Z)-1-(pyridin-2yl)-4-(quinolin-2-yl)buta-1,3-diene-2,3-diol tautomers are more stable in vacuum than their other tautomers. This was explained by strength of the intramolecular hydrogen bonds and aromatic character of the (quasi)rings. We know of no buta-1,3-diene-2,3-diol with a measured enthalpy of formation data, or for that matter any butadienediol. For a calculational study related to the energetics of the isomeric dihalobutadienes, see [307]. For an experimental study summarizing the enthalpies of formation of the three isomeric hydroxybuta-1,3-dienes, see [308]. In this study, there was but one ene-diol derivative discussed, ethene1,2-diol. Vasilescu and Adrian-Scotto [309] in their paper review the development of quantum molecular modeling from historical approach and atom concept to two essential ways used today, the ab initio and DFT methods with which, among others, conformational analysis, electrostatics, molecular spins and radicals, infrared and Raman spectra, thermochemistry, and electrophilicity properties can be derived. The issue and the 2010 volume conclude with a book review written by Hargittai [310] of the book by Andreas ckel (18961980): From Physics to Karachalios Erich Hu ckel, Quantum Chemistry. In this biography of Erich Hu his life, research and achievements, in particular in the eld of quantum chemistry and its early development, are documented. References
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