In the Laboratory

Coordination Chemistry of Pd(II) Complexes with P-Donor Ligands

An Introduction to Synthesis and Structural Characterization in Coordination Chemistry
Esteban P. Urriolabeitia Departamento de Qumica Inorgnica, Instituto de Ciencia de Materiales de Aragn, Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain The phosphorous-containing ligands, such as phosphines (PR3) or diphosphines [R 2P(CH 2)n-PR2 ] (R = alkyl or aryl; n = 1, 2, 3, ) are one of the most widely used groups of ligands in palladium chemistry (1). Complexes containing the PdPR3 or Pd[R2P(CH 2)nPR2P,P] units are known for all the most common oxidation states of the Pd atom (2). They have shown important and useful applications as starting compounds in coordination and organometallic chemistry (3, 4) and as catalysts in organic synthesis (4, 5). For instance, complexes such as PdX 2(PR3)2 or PdX2(diphosphine) are used in the synthesis of several Pd(I) and Pd(0) derivatives, clusters of mixed valence, etc. ( 3, 4, 6). Moreover, these PdX2 L2 (L = phosphine) complexes are recognized catalysts in a very wide range of organic reactions, such as molecular rearrangements ( 7), substitution processes at allylic carbons (8), coupling of alkene and alkyne groups (9), hydrogenation of alkynes, dienes, and alkenes (10), and carbonylation and oxidation of several substrates (11). Complexes such as Pd(PR3 )n (n = 2, 3, 4) have had wide use in the catalysis of hydrosilylation reactions (12, 13 ), dimerizations, and oligomerizations. We propose here the synthesis and complete characterization of a family of Pd(II) complexes containing two or more PdP bonds as a laboratory experiment complementary to a classroom course on coordination chemistry. The synthesis section has the advantage that all of the compounds prepared are air-stable, both in the solid state and in solution (avoiding the use of special apparatus), and they can be prepared under mild conditions in short reaction times. Characterization includes the use of several instrumental techniques (molar conductances in solution, IR spectra, 1H and 31P{1H} NMR measurements; see details in section on experimental procedures) that allow students to become familiar with the more usual structural methods and with the interpretation of the resulting data. This laboratory work can be done individually. We recommend five periods of four hours period to complete it. The
PdCl2 2 tht PdCl2(tht)2 Ph3P Pd Ph3P PPh3 Cl (BF4) PPh3 2 tht 2 PPh3 PdCl2(PPh3)2 AgCl AgBF4 AgCl dppm AgBF4 PPh3 Pd Cl PPh3 Me Tl(acac) TlCl Ph3P Pd Ph3P O Me O (BF4) (BF4)2 Ph3P Ph3P Pd PPh2 CH2 (BF4)2 PPh2

reactions illustrated in Figure 1 summarize the practical work and introduce to the student some common concepts and skills in coordination (and in organometallic) chemistry:
substitution of weakly coordinated ligands generation of coordinatively unsaturated species symmetrical cleavage of halogeno-bridged dimers chelate effect exclusion of light in reactions involving silver-containing reactants

Experimental Procedures CAUTION : THT (tetrahydrothiophene) is toxic and has an unpleasant odor; it should be handled with care and reactions involving it must be carried out in an efficient ventilation hood; Tl(acac) (acac = acetylacetonate) is also toxic and should be handled with care; the use of gloves and protective glasses is highly recommended.

General Molar conductance (M) measurements were performed on a Philips PW9509 digital conductivity meter in acetone solutions (ca. 5 104 M). IR spectra (4000200 cm1) were recorded on a Perkin-Elmer 883 spectrophotometer, using a Nujol mull between polyethylene sheets. 1H and 31P{1H} NMR spectra were recorded on a Varian Unity-300 using CDCl3 as solvent and referenced to TMS and H3PO4 (85%), respectively. Tl(acac) (14 ) and DPPM [Ph 2 PCH2 PPh2 , bis(diphenylphosphino)methane] (15) were prepared as previously described, with slight modifications. AgBF4 , THT, and PPh3 (Fluka), and PdCl 2 were used as received. Solvents used do not require a high degree of purity and were used as received [Probus (R. A.) and Carlo Erba (R.)]. Preparation of Compounds 15 Preparation of [Pd( -Cl)(PPh3)2]2(BF4)2 (1) Synthesis of the starting compound (1) involves two preliminary steps: a. Synthesis of trans-PdCl2 (THT)2. To a suspension of finely ground PdCl2 (0.500 g, 2.82 mmol) in 30 mL of CH2 Cl2, THT (0.50 mL, 5.67 mmol) was added. The mixture was stirred at room temperature for 3 h giving a red solution, and then filtered to remove traces of metallic palladium. The resulting solution was evaporated to dryness and the residue was washed with n-hexane (50 mL) giving the complex transPdCl2(THT)2 as an orange-red solid, which was filtered, gently washed with n-hexane (3 20 mL) to remove the free THT, and air dried. Obtained: 0.85 g (85% yield). b. Synthesis of trans-PdCl2 (PPh3)2 . The PdCl2 (THT)2 obtained (0.85 g, 2.40 mmol) was dissolved in 30 mL of CH2Cl2, and PPh3 (1.26 g, 4.80 mmol) was added. A yellow solid precipitated immediately. The suspension was stirred for an additional 30 min at room temperature, then filtered, washed three times with 10-mL portions of Et 2O, and air dried, giving trans-PdCl2(PPh 3)2 as a deep yellow solid. Obtained: 1.60 g (95% yield).

(2)
Ph3P 1/2 Ph3P dppm PPh3 Pd Cl

(5)

(1)
Ph3P Pd Cl PPh2 CH2 (BF4) PPh2

(3)

(4)

Figure 1. Scheme of the reactions performed for the synthesis of complexes 15.

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Table 1. Data for Complexes 15
Complex 1 IR (, cm1) 1061 {BF4}, 538, 523, 513, 499 {PPh3}, 309 {st(Pd-Cl)br} 2 1054 {BF4} 539, 521, 513, 500 (sh), 493 {PPh3}, 316 {st(Pd-Cl)t} 3 1058 {BF4
}, 1H NMR (, ppm; J , Hz) 31P{1H}

NMR (, ppm; J, Hz)

Molar conductance (M, 1cm2mol1) 253

(P) = 38.31 (Pa, d) = 29.66 (Px, t) = 32.49

2J (P P ) a x

129

= 15.44 103

545, 522, 511,

(Pa, d) = 22.22, 2J (PaPx) = 465 (Pm, d) = 38.72, 2J (PmPx) = 81 (Px, dd) = 52.71 (CH-acac, s) = 5.41 (CH3-acac, s) = 1.49 (C6H5, m) = 78 (Pa) = 24.26 (Px) = 26.65
2J (P P ) a x

495, 481, 477 {PPh3 + DPPM} 316 {st(Pd-Cl)t} 4 1564, 1522, 1516 {(C=O), acac}, 1058 {BF4}, 749 {(C-H), acac}, 545, 525, 516, 498 {PPh3} 5 1063 {BF4}, 532, 521, 506, 495, 472, 461{DPPM + PPh3}

(P) = 35.86

134

Insufficiently soluble

= 360; 2J (Pa-Px') = 22

I 2J (PaPa') + 2J (PxPx')| = 77

c. Synthesis of [Pd( -Cl)(PPh3 )2 ]2 (BF4 )2 . A suspension of trans -PdCl2 (PPh3 )2 (1.50 g, 2.13 mmol) in 130 mL of CH2Cl2 was treated with AgBF 4 (0.416 g, 2.13 mmol). This mixture was stirred at room temperature for two hours with exclusion of light. The initial yellow suspension gradually changed color, giving a white precipitate of AgCl and an orange solution. After removal of the AgCl the orange solution was evaporated to dryness and the residue treated with 40 mL of n -hexane, giving the complex [Pd( Cl)(PPh3)2]2(BF4)2 (1) as a lemon-yellow powder, which was filtered, washed with n -hexane (20 mL), and air dried. Obtained: 1.500 g (93% yield). Preparation of [PdCl(PPh3)3](BF 4) ( 2) Complex 1 (0.225 g, 0.149 mmol) was dissolved in 25 mL of CH 2Cl2 and to the resulting solution PPh 3 (0.078 g, 0.298 mmol) was added. The initial lemon-yellow solution immediately became deep yellow. The solution was refluxed for 1 hour. After cooling, the solvent was evaporated to dryness and the residue treated with Et 2O (25 mL) giving 2 as a yellow solid, which was collected and air dried. Obtained: 0.276 g (91% yield). Preparation of [PdCl(PPh2CH 2PPh 2-P,P)(PPh3)](BF4) (3) Complex 1 (0.225 g, 0.149 mmol) was dissolved in 25 mL of CH2 Cl2 , and DPPM (0.115 g, 0.298 mmol) was added to the solution. An orange solution was obtained, which was refluxed for 1 h. After cooling, the solvent was evaporated to dryness and Et2O (20 mL) was added to the residue. Continuous stirring gave 3 as an orange solid, which was filtered, washed twice with 10-mL portions of Et2 O, and air dried. Obtained: 0.238 g (91% yield). Preparation of [Pd(acac-O,O)(PPh3)2](BF4) (4) Complex 1 (0.225 g, 0.149 mmol) was dissolved in 25 mL of CH2Cl2 and Tl(acac) (0.091 g, 0.298 mmol) was added to the solution. A white precipitate of TlCl was formed instantaneously. The suspension was stirred at room temperature for 30 min and then filtered. The resulting yellow solution was evaporated to dryness and n-hexane (20 mL) was added to the oily residue. Continuous stirring gave 4 as a yellow solid, which was filtered and air dried. Obtained: 0.161 g (66% yield).

Preparation of [Pd(PPh2CH2PPh 2-P,P )(PPh3)2](BF 4) 2 (5) Complex 1 (0.250 g, 0.166 mmol) was suspended in 35 mL of acetone, and AgBF4 (0.065 g, 0.332 mmol) was added. The mixture was stirred for 1.5 h at room temperature with exclusion of light and then filtered to remove the AgCl precipitate. The freshly obtained solution of [Pd(PPh3)2 (acetone)2 ](BF4)2 was treated with DPPM (0.128 g, 0.332 mmol) and stirred for another 45 min. During this time, a white solid (5) precipitated, which was collected, washed with acetone (3 3 mL), and air dried. Obtained: 0.168 g (43 % yield). Results and Discussion The reaction between PdCl2 and THT (1:2 molar ratio) leads to the formation of the complex trans-PdCl2(THT)2. By reaction of this complex with PPh3 (1:2 molar ratio), the weakly coordinated ligand THT is easily displaced from the starting compound by the PPh3 ligand, and the complex trans-PdCl2 (PPh3)2 is obtained in good yield. Further reaction of the complex trans-PdCl2 (PPh3)2 with AgBF 4 (1:1 molar ratio) produces the dinuclear complex 1. Such complexes, with -halogen bridges, are quite reactive and are convenient precursors in the synthesis of other Pd(II)-complexes. We then perform two types of synthetic exercises: 1. Cleavage of the ( -X)2 bridging unit with P-donor ligands. Cleavage with monodentate ligands such as PPh 3 gives the mononuclear complex (2 ) and cleavage with bidentate ligands such as DPPM gives the mononuclear complex (3). For complex 3, the chelate effect of the DPPM ligand promotes the displacement of a PPh3 ligand and the bidentate-P,P coordination of the DPPM, instead of the monodentate-P coordination derived from the simple breakage of the (-X)2 unit. 2. Displacement of the -X ligands by their precipitation as insoluble salts and generation of the coordinatively unsaturated species cis-[Pd(PPh 3)2]2+. In this way, the reaction between 1 and Tl(acac) produces the precipitation of TlCl and the coordination of the acac- ligand to the cis[Pd(PPh3)2]2+ group, giving complex 4. The reaction of 1 with AgBF4 in acetone produces the precipitation of AgCl and the solvated complex [Pd(PPh 3)2 (acetone)2 ]2+, which subsequently reacts with DPPM affording complex 5.

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The stereochemistry of complexes 15 can be inferred from the analysis of their molar conductance values (acetone solutions) and IR and NMR spectra (Table 1). Thus, for complex 1, the absorption st(Pd-Cl) at 309 cm1 suggests a bridging coordination of the chlorine ligands ( 16) and four absorptions in the 550500 cm1 region indicate the presence of PPh3 ligands (17). A single resonance in the 31P{1H} NMR spectrum is observed. These data, together with the observed molar conductance in acetone solution (1:2 electrolyte, see Table 1) (18) supply the information required to deduce the stereochemistry of complex 1 and to understand its further reactivity. Complex 2 shows a very complicated pattern of absorptions in the 550500 cm1 region (presence of phosphines) and a strong absorption at 316 cm1 [st(Pd-Cl)]. This shift to higher energies suggests a change in the coordination mode of the Cl ligand. Moreover, the analysis of the 31P{1H} NMR spectrum provides additional valuable information: the observation of an A 2X spin system points out the existence of a Pd(PPh3 )3 unit. These data, together with the measured molar conductance (typical for 1:1 electrolytes) (18), allow an unequivocal determination of the structure of 2 as that depicted in Figure 1. For complex 3, the meaning of the observed changes in the IR spectrum and the analysis of the 31P{1H} NMR spectrum (AMX spin system, Fig. 2) can be done by the students as an exercise, taking into account the comments above for complex 2. For complex 4, two strong absorptions at 1564 and 1522 cm1 in the IR spectrum are due to the chelate acac ligand O,O -coordinated (19) and four absorptions in the 550500 cm1 region show the presence of phosphine ligands (17 ). These data suggest the structure depicted in Figure 1 for complex 4. In agreement with this structure, the 1H NMR spectrum shows a sharp singlet at 5.41 ppm [C H -(acac)] and another singlet (relative intensity 1:6) at 1.49 ppm [CH 3-acac], showing the chemical equivalence of the two CH3 groups, and the 31P{1 H} NMR spectrum shows a single resonance, resulting from the chemical equivalence of the two PPh3 groups. Finally, the unequivocal elucidation of the molecular structure of 5 comes from the analysis of the 31P{1H} NMR spectrum, which is a clear example of a deceptively simple AA XX spin system (Fig. 3) (20), thus giving proof of its mononuclear nature. Acknowledgments I thank J. Fornis and R. Navarro for helpful discussions and DGICYT (Spain) for financial support (Project PB92-0364). Literature Cited
1. Hartley, F. R. The Chemistry of Platinum and Palladium ; Applied Science: London, 1973. 2. McAuliffe, C. A.; Levanson, W. Phosphine, Arsine and Stibine Complexes of the Transition Elements; Elsevier: Amsterdam, 1979. 3. Albeniz, A. C.; Espinet, P. Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; John Wiley & Sons: West Sussex, England, 1994; Vol. 6, pp 3010 and following. 4. Suggs, J. W. Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; John Wiley & Sons: West Sussex, England, 1994; Vol. 6, pp 3023 and following. 5. Heck, R. F. Palladium Reagents in Organic Synthesis ; Academic: London, 1985. 6. Barnard, C. F. J.; Russell, M. J. H. Comprehensive Coordination Chemistry; Wilkinson, G.; Gillard, R. D.; McCleverty, J. A., Eds.; Pergamon: Oxford, 1987. Vol. 5, pp 1099 and following. 7. Trost, B. M. Acc. Chem. Res. 1990, 23, 34. 8. Yamaguchi, M.; Shima, T.; Yamagishi, T.; Hida, M. Tetrahedron Lett. 1990, 31, 5049. 9. Trost, B. M.; Shi, Y. J. Am. Chem. Soc. 1992, 114, 791. 10. Stern, E. W.; Maples, R. K. J. Catalysis 1972, 27, 120; ibid., p 134.

Figure 2. 31P{1 H} NMR spectrum of complex 3 .

Figure 3. 31P{1 H} NMR spectrum of complex 5 .

11. Spencer, A. Comprehensive Coordination Chemistry ; Wilkinson, G.; Gillard, R. D.; McCleverty, J. A., Eds.; Pergamon: Oxford, 1987; Vol. 6, pp 229 and following. 12. Tsuji, J.; Hara, M.; Ohno, K. Tetrahedron 1974, 30, 2143. 13. Mitchell, T. N.; Amamria, A.; Killing, H.; Rutschow, D. J. Organomet. Chem. 1983, 241, C45. 14. Taylor, E. C.; Hawks, G. H., III; McKillop, A. J. Am. Chem. Soc. 1968, 90, 2421. 15. Issleib, K.; Muller, D. W. Chem. Ber. 1959, 92, 3175. 16. Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds; Wiley: New York, 1986; pp 328331. 17. Mastin, S. H. Inorg. Chem. 1974, 13, 1003 and refs cited therein. 18. Geary, G. Coord. Chem. Rev. 1971, 7, 81. 19. Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds; Wiley: New York, 1986; pp 259263. 20. Gnter, H. Angew. Chem. Int. Ed. Engl. 1972, 11, 861.

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