Transition metal acetates

D. A. EDWARDS AND R. N. HAYWARD

School of Chemistry and Chernical Engitzeering, Bath U~liuersify of Tecl~nology, Bath, Sonierset, England Received May 3, 1968

Some anhydrous transition metal acetates (Mn(II), Co(II), Cu(II), Ni(II), Zn(II), Ag(I), Mo(II), Ce(III), La(II1)) have been prepared and their infrared spectra measured in the solid state. The infrared spectra have been related to established modes of bonding of the acetate group to metals. Thermal decompositions of the anhydrous acetates have been investigated by thermogravimetric analysis; magnetic moments and visible spectra have been measured.
Canadian Journal o f Chemistry, 46, 3443 (1968)

Introduction Rao and co-workers (I) have recently reported infrared and thermal decomposition data on anhydrous acetates of the lanthanides, lead(I1 and IV) and copper(I1). We have also obtained results upon some of these compounds together with data on several other transition metal anhydrous acetates. Our infrared results point to the unreliability of using the v,,,~(COO)vSy,(COO) frequency separation to determine the mode of coordination of the acetate group to the metal, although such a method has been used frequently in the past (2). Visible reflectance spectroscopy and magnetic measurements have been used, where appropriate, to show the coordination number of the metal in the anhydrous acetates and to place the acetate group in the spectrochemical and nephelauxetic series. Experimental
The anhydrous acetates of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), La(III), and Ce(II1) were prepared by refluxing the commercially available hydrates with a large excess of a 3 :2 (vol./vol.) acetic acid - acetic anhydride TABLE I Analytical results

mixture. After cooling, the insoluble products were filtered, washed with the solvent mixture followed by sodium-dried ether, and finally pumped under vacuum for 2 h at room temperature. Nickel acetate was found to have 4- mole of associated acetic acid after this preparation and pumping, this acid being removed by heating at 200" under vacuum. The other acetates were not similarly solvated. Molybdenum(I1) acetate was prepared from the carbonyl (3) and silver(1) acetate was commercially available. Analytical results are given in Table I. Infrared spectra were recorded as Nujol, hexachlorobutadiene, and fluorlube mulls using a Perkin-Elmer 237 grating spectrophotometer. Visible spectra were recorded using a Unicam S P 500 spectrophotometer, the diffuse reflectance spectra being obtained using the standard attachment. Magnetic measurements were determined by the Gouy method at room temperature. TABLE I1 Infrared frequencies (cm-')
.

Acetate

VSY,(COO)

coo)

AV

% Metal
Compound Found Calcd.

% Acetate Found Calcd.

Thermogravimetric studies were carried out using a Stanton TR 1 thermogravimetric balance heating at 4" per minute over the range room temperature to 1000. Products remaining at the end of such decompositions were analyzed for metal content and shown to be the oxides mentioned in Table IV.

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Results and Discussion I~grared Spectra The free acetate ion, symmetry C,,, has 15 infrared active fundamentals, all of which, except the v6 torsional mode, have been observed (4, 5). Four modes of coordination to metals (1-4) are possible (2b), but since the symmetry of the free ion is low no great differences in the infrared spectrum would be expected for each type. The v3 (v,,,(COO)) and v, (V,,~,(COO)) frequencies, and their difference, Av, for the acetates studied here, are shown in Table 11.

It has been suggested (2) that where the acetate is a unidentate ligand (2) a divergence of V,,~,,(COO) and vsY,(COO), compared with the free ion, is expected due to a decrease in the bonds. Thus the equivalence of the C-0 VaSym (COO)-vSy,(C00) separation for [CO(NH,),OCOCH,]~+ is 223 cm-' (2a) compared with 153 cm-' for sodium acetate of type (1). Of the compounds studied here, the tetrahydrated nickel and cobalt acetates are known to be octahedral and the corresponding manganese compound is expected to be the same, the metals being coordinated with four oxygens from the water molecules and two oxygen atoms from unidentate acetate groups (6). A large V,,~,(COO)vSym(COO) separation is, however, not observed in the infrared spectrum; the small separation found could be due to hydrogen bonding with the water molecules making the C-0 bonds more equivalent than expected for unidentate acetate coordination. In the corresponding anhydrous acetates the mode of coordination of the acetate group to the metal must change since the visible spectra and magnetic measurements show the acetates to be still octahedral and hence polymeric. Since overall there are only two acetates per metal atom both oxygens of the acetate group are expected to be involved in the coordination and the acetates must bond to more than one metal atom by bridging. The V,,~,(COO)vsym(COO) separation, however, is unexpectedly

greater than in the hydrated unidentate acetate cases. We are unable to state if all the acetate groups in the octahedral polymers are bridging (4) or whether some are chelating (3), since in the two cases we have studied where all the acetate groups are known to be bridging, copper(I1) (7) and molybdenum(l1) (8), a very similar degree of v,,,,(COO)-v,ym(COO) separation is found. For bridging or chelating symmetrical acetate structures both COO stretching frequencies are shifted in the same direction on changing the metal, so the separation will not be greatly different from that of the free ion. Tlie structure of dihydrated zinc acetate is known (9) to be octahedral, the coordination to the metal consisting of two oxygen atoms from the two water molecules and four oxygens from two chelating acetate groups. We find, again, the infrared spectrum cannot be regarded as diagnostic of such a n acetate coordination. Anhydrous zinc acetate shows an almost identical v,,ym(COO)-v,,,(COO) separation, so the acetate could be tetrahedral with just two chelating acetate groups, but an octahedral coordination achieved by bridging and shared acetates cannot be ruled out. Our results for anhydrous lanthanum(II1) acetate are similar to those published by Raoet al. (I) except we find a lower vSym(COO) frequency. We have also recorded the infrared spectrum of cerium(II1) acetate (10) which Rao and coworkers.did not include in their study. Rao and co-workers (1) suggested that the acetate groups in lanthanum(II1) acetate were unidentate, but the results, in our opinion, do not require this, and indeed, in view of the high formal positive charge on the metal and the favoring of high coordination numbers by the lanthanide elements, chelation or bridging acetate groups would seem more likely. Thus we are of the opinion that the use of the infrared v,,,,(COO)-vSym(C00) separation as a means of assessing the mode of coordination of acetate groups to metals must only be used with extreme caution and cannot be . regarded as universally valid. Visible Spectra Diffuse reflectance visible spectra have been measured for anhydrous cobalt(II), nickel(II), and copper(I1) acetates, the results and assignments being given in Table 111. The spectra of the cobalt and nickel salts are typical of octahedral

EDWARDS AND HAYWARD: TRANSITION METAL ACETATES

TABLE 111 Visible spectra and magnetic moments Visible spectra

p (B.M.) at
-

Acetate

room temp.

Method D.R."

Peak (cm-')
17 400 (sh)

Assignment

D.R. Sol.
1.39

:i 2; :i :z

(sh)} 17 400 (sh)

Diamagnetic Diamagnetic 2.30 0.25

D.R. Sol.

(sh)} 13 500 14 600 25 000 13 700 14 800 25 000 14 800 (br) 14 300 (br)

0D.R. diffuse reflectance. bSol. solution i n acetic acid - acetic anhydride mixturt coordination of these metals. The splitting of the band centered at 18 900 cm- for cobalt(I1) acetate has been noticed for many other octahedral cobalt(11) systems and attributed (1 l ) to various sources. In the present example, the shoulder could be tentatively assigned (1 1) to the 'T,,(H) + 4T?,(F) transition, this having gained with the spin-allowed transiintensity by m~xing tion. From these assignments for cobalt(I1) acetate 10 Dq, the Racah parameter B and the nephelauxetic ratio P3, have been calculated using the method of Underhill and Billing (12). 10 Dq has been found to be 9250 cm- and B 790 cm-'. Using the free gaseous ion B value of 972 cm-', p3, is found to be 0.81. Calculations (12) of 10 Dq, B, and P,, for nickel(I1) acetate give the values 8420 cm-', 916 cm-', and 0.89 respectively, using the free ion B value of 1030 cm-'. These results place the acetate group close to water in both the spectrochemical and nephelauxetic series (for water 10 Dq = 8600 cm-'; B = 925 cm-'; and P3, = 0.88). Manganese(I1) acetate has only low intensity spin-forbidden bands in the visible region typical of high-spin octahedral manganese(I1).

'

'

spin cobalt(II), and nickel(I1). Manganese(I1) acetate has a moment virtuallv identical with the 'spin-only' moment, there being n o orbital contribution, but cobalt(I1) and nickel(I1) acetates have moments above the 'spin-only' values due to orbital contributions, from the 4Tl,(F) ground state and 4T excited states for cobalt, and only from the 3T excited state and not from the 3A,, ground state for nickel. The magnetic moment of copper(I1) acetate agrees with previous results (13) but the magnetic moment of dimeric molybdenum(I1) acetate (d4) is grossly reduced to 0.25 B.M., indicating a much greater metal-metal interaction than in the isostructural copper acetate. This is in agreement with X-ray results (8) which show a very short Mo-Mo bond length of 2.1 1 8L indicating bond multiple bonding, whereas the Cu-Cu length in the dihydrate (7) is 2.6 8L in length, probably indicating weak 6 copper-copper bonding. The magnetic moment of cerium(II1) acetate is in the range expected for cerium(II1) compounds, ground state 'F,,,, whose magnetic results can be treated to a good approximation by L-S coupling and are essentially independent of surrounding ligands and stereochemistry. Thermal Decompositions (14) Thermogravimetric analysis (t.g.a.) results are shown in Table IV, the heating being carried out under normal atmospheric conditions.

Magnetic Measurements The room temperature magnetic moments are given in Table I11 and are typical of octahedral coordination for high-spin manganese(Il), high-

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TABLE IV Therrnogravimetric results

Acetate

1st decomposition stage

weight change

2nd decomposition stage

3rd decomposition stage

weight change

% weight change
Compound Obsd. Calcd.
-

Compound

Obsd. Calcd.
56.8 59.1 54.8 57.7 14.2 14.5 61.8 62.1 55.1 55.6 31.2 32.7 41.5 41.5 45.4 45.7 35.8 35.4

Compound Obsd. Calcd.

Mn304
c 0 3 0 4

Mn(I1) MnO Co(II) COO Ni(II).0.5CH3COOH Ni(CH,COO), Cu(I1) CuzO + Cu

ZnO MooJ
Ag
aNo solid remains: MOOJ

Mnz03
c 0 2 0 3

NiO

CuO La203
-

52.8 50.5 62.4 56.0 48.4

-

54.4 53.1 63.9 56.2 48.4

54.6 51.9

55.9 54.6

La202C0, CeO,
-

volatile.

The t.g.a. of anhydrous lanthanum(II1) acetate Decompositions of zinc(I1) and molybdeagrees well with the results of Rao et al. (I), the num(I1) acetates lead to the formation of ZnO oxycarbonate, La20,C0,, being completely and MOO, at 350 and 280" respectively as sole formed at 480" and decomposing to La20, at products, whereas from silver(1) acetate only the 875". No evidence for the previously reported metal is produced by 280, there being no evi(15) oxyacetate was found. An oxycarbonate dence of oxide formation at lower temperatures. stage was not found in the t.g.a. of cerium(II1) acetate, the only product being the formation of 1. K. C. PATIL,G. V. CHANDRASHEKHAR, M. V. cerium(1V) oxide at 500". Both manganese@) GEORGE, and C. N. R. RAO. Can. J. Chem. 46,257 and cobalt(I1) acetates decompose to the mon(1968). 2. (a)K. NAKAMOTO, F. FUJITA, S. TANAKA, and M. oxides at ca. 350, which are then oxidized KOBAYASHI. J. Am. Chem. Soc. 79, 4904 (1957). completely to M 2 0 3 stages by 600" followed by (6) K. NAKAMOTO. Infrared spectra of lnorganlc M304 stages at 950, although minor weight and co-ordination compounds. John Wiley and Sons, Inc., New York. 1963. change discrepancies for the individual stages E. BANNISTER, and G. WILKINSON. 3. T. A. STEPHENSON, indicate that the decomposition stages overlap to J. Chem. Soc. 2538 (1964). and H. J. BERNSTEIN. Can. J. Chem. 34, 4. K. ITOH some degree, probably due to the heating rate of 170 (1956). the apparatus. The hemi-solvate of nickel(I1) 5. K. J. WILMSHURST.J. Chem. Phys. 23,2463 (1955). acetate loses the attached acetic acid completely and F. R. L. SCHOENING. Acta 6. J. N. VAN NIEKERK Cryst. 6, 609 (1953). in air by 280" with the formation of the anhydrous and F. R. L. SCHOENING. Acta 7. J. N. VAN NIEKERK acetate, but from the subsequent weight change Cryst. 6, 227 (1953). the acetate appears to decompose to a mixture of J. Am. Chem. Soc. 87, and R. MASON. 8. D. LAWTON 921 (1965). the metal and nickel(I1) oxide, the metal present 9. J. N. VAN NIEKERK, F. R. L. SCHOENING, and J. H. being finally oxidized to the oxide completely by TALBOT. Acta Cryst. 6, 720 (1953). 10. T. MOELLER, V. GALASYN, and J. XAVIER. J. Inorg. 600". Chem. 15, 259 (1960). Copper(I1) acetate starts to decompose at 230" 11. Nucl. J. Chem. Soc. A, A. B. P. LEVER and D. OGDEN. to a mixture of copper metal and copper(1) oxide, 2041 (1967). and D. E. BILLING. Nature, 210, both being completely oxidized to copper(I1) 12. A. E. UNDERHILL (1966). oxide by 535". No evidence for the formation of 13. 834 M. KATO,H. B. JONASSEN, and J. C. FANNING. copper(1) acetate was found by this method, but Chem. Rev. 64, 99 (1964). C. DUVAL. Inorganic therrnogravimetric analysis. 14. a careful decomposition of copper(I1) acetate in 2nd ed. Elsevier Publ. Co., Inc., Amsterdam. 1963. vacuo at 220" leads to the formation of a very 15. V. N. MASKIMOV and K. N. SEMENENKO. Zh. hygroscopic colorless sublimate of copper(1) Neorg. Khim. 3, 1468 (1958). and A. V. HARCOURT. J. Chem. Soc. acetate. Since little is known of the chemistry of 16. A. ANGEL 1385 (1902). this compound (16) it is, at present, being fully studied.