Inorganic Chemistry, Vol. 11, No. 7, 1972 1591
VANADYL DITHIOPHOSPHINATE COMPLEXES
CONTRIBUTION FROM THE DEPARTMENT OF CHEMISTRY, UNIVERSITY O F ALBERTA,EDMONTON, ALBERTA, CANADA
Metal Complexes of Substituted Dithiophosphinic Acids. 111. Vanadyl Complexes' BY R. G. CAVELL,* E. D. DAY, W. BYERS,
AND
P. M. WATKINS
Received July 13, 1971 The preparation and characterization of dithiophosphinato complexes of oxovanadium(IV), OV(SZPXZ)Z (X = CH3, C6Ha, CFg, OC2H,, F), are described. Solution and glass epr spectra show hyperfine coupling to 31Pand 51V; the former is isotropic a t 77°K in the CH3, CeH6, and OCzHj cases. Difficulties were experienced in obtaining glass spectra of X = F and CF3 complexes and these two systems also show anomalous bulk magnetic susceptibility behavior (over the temperature range 90-303OK) which is thought to arise from interactions between molecules through the formation of VOV chains. Infrared spectra of X = F and CFf complexes show a large reversible shift of the VO absorption between solution and solid states which substantiates this interpretation. Electronic spectra are discussed with reference to the current state of knowledge of V 0 2 + spectra. Infrared spectra were obtained on Perkin-Elmer 421 and BeckIntroduction man IR-11 instruments. Ultraviolet and visible spectra were Although the epr spectrum of the complex OV[S2Pmeasured with a Cary 14 spectrometer, and diffuse reflectance (OC2H5)2]2has been reported several times,2--8 isolaspectra were obtained with the Cary 1411 reflectance attachment. Gaussian analyses of spectra were performed using the program tion of the compound was apparently not achieved. B I G A U S S . ~ ~ Epr spectra on both solutions and glasses were obThe difficulty in isolation has even been taken to imply tained on a Varian X-band spectrometer. Numerical data from inherent instability of the ~ o r n p l e x . ~ We wish to dissolution spectra were derived by fitting simulated spectra to obpel impressions of unusual instability of the complexes served spectra using the computer program SIMESRLQ.~~ Mass spectra were obtained by means of the direct probe sample inserin this oxovanadium(1V) system by describing the tion system of the AEI MS9 mass spectrometer operating a t ready preparation and physical properties of the series 70 eV. l'ariable-temperature magnetic susceptibilities were of dithiophosphinate complexes OV [SZPXZIZ, where X = measured by the Faraday technique using a cryostat of our own CHI, CGH5,OC2Hb,F, or CF3, as part of our continuing construction.'6 The magnetic field was calibrated with HgCoinvestigation of the transition metal complexes of this (SCn')r prepared as described.'* Analyses (C, H , and S) were performed by the microanalytical service of the University of series of ligands.' A preliminary account of this work Alberta and by Schwarzkopf Laboratories, Woodside, N. Y . has been presented.' Epr data have also been given The CFa compound was analyzed by alkaline hydrolysis, each for the complexes with the identical ligand substituents (CF3)1PS2- unit yielding one unit of CF3H.l0 l6 Final purificaX = X' = C3H7and C 6 H ~and for the complex contion of fluoro and CFBcomplexes was effected by fractional subtaining two different substituents on phosphorus : X = limation in a vertically mounted long glass tube.' Analytical data are given in Table I. C,H5 and X' = OC2H5.5 The preparation and characterization of the X = C8He8 and X = C2Hb and C ~ H T ~ Synthesis of the Complexes. (a) O V [ S Z P ( C F ~2.) ~ ] (i) From Aqueous Solution.-Bis(trifluoromethy1)dithlophosphin~c complexes were also reported while this work was in acid, (CF3)zPS2H (0.402 g), was condensed into a solution of preparation. 0.09 g of XaaCO3 in 0.5 ml of water contained in an epacuated vessel equipped with a cooled sublimation probe and the solution was stirred for 1 hr. The vessel was opened and vanadyl sulfate, VOSOI.~HZO (0.172 g), was added to the solution and the entire Volatile, air-sensitive compounds, particularly derivatives of the fluoro and trifluoromethyl acids, were handled in a convenapparatus was again evacuated. The blue, aqueous solution was tional vacuum system greased with Apiezon N stopcock grease. stirred a further 30 min, and then the volatile materials were Other systems were handled in air or nitrogen-filled glove bags removed under vacuum with the probe cooled to 10". After ~ of the water had been removed by this procedure, the with typical bench-top techniques. Syntheses of H S Z P ( C F ~ ) ~ ' ~ - 'most and HS2PFzia-ls have been described elsewhere. vessel was warmed to 60" and a black sublimate was collected on the probe. The ir of a iYujol mull of the black sublimate showed the following bands (em-'): 3250 (vb), 1610 (m), 1297 (1) P a r t 11: R. G. Cavell, W. Byers, E. D. Day, and P. VI. Watkins, Inorg. Chern., 10, 2716 (1971). (w), 1212 (sh), 1194 (s), 1178 (s), 1163 (s), 1130 (sh), 1012 (m),973 (2) N. S. Garif'yanov and B. M . Kozyner, Teov. E k s p . Khim., 1, 525 (w), 863 (m), 771 (w), 726 (mw), 693 (m), 680 (w), 646 (w), (1965). 613 (s), 535 (m), 472 (m). This sublimate was transferred in a (3) N. S. Garif'yanov, B . M . Kozyner, and I. F. Gainullin, Z h . Slvukl. drybag and resublimed [subl p t 52" ( l o w 2Torr)] to sield about Khim., 9, 529 (IQ68). 0.2 g of VO[SIP(CFI)Z]Z.Anal. Calcdig for OVS~PZCJ?IZ (nzle (4) (a) C. Furlani, A . A. G. Tomlinson, P. Porta, and A. Sgamellotti, 532.7555): S, 24 17; CF3, 26.25 Found ( m / e 532.7550): J . C h e m . 5'06. A , 2929 (1970); (b) C. Furlani, P. Porta, A . Sgamellotti, and S, 25.32; CF3 (as CF3H), 26.0. A. A. G. Tomlinson, J . Chem. Soc. D ,1046 (1969). (5) I. V. Obchinnikov, I. F. Gainullin, N. S. Garif'yanov, and B. M . (ii) From Vanadium Pentoxide.-Excess (CFa)zP(S)SH was Kozyrev, Dokl. A k a d . N a u k SSSR, 191, 395 (1970). condensed onto 1 ' 2 0 5 and the acid was refluxed under vacuum for (6) J. R . Wasson, Inovg. Chem., 10, 1531 (1971). We thank D r . Wasson 24 hr in an evacuable vessel equipped with a sublimation probe. for sending us a preprint of this paper prior to publication. With the probe cooled to lo", the volatile products were then ( 7 ) Presented t o the X I I t h International Conference on Coordination removed under vacuum. Warming the base of the sublimer t o Chemistry, Sydney, Australia, Aug 1969. 70' caused a brown material to collect on the cooled probe. (8) A. Muller, V. V. Krishna Rao, and E. Diemann, Chem. B e y . , 104,
Experimental Section
461 (1971). (9) H. Hertel and W. Kuchen, ibid., 104, 1740 (1971). ( I O ) R. C. Dobbie, L. F. Doty, and R. G. Cavell, J . Amer. Chem. Soc., 90, 2015 (1968). (11) K. Gosling and A. B. Burg, ibid.. 90, 2011 (1968). (12) R. G. Cavell and A. A. Pinkerton, ibid., 9S, 2384 (1971). (13) T. L. Charlton and R. G. Cavell, Inorg. Chem., 8 , 281 (1969). (14) R . W. Mitchell, M . Lustig, F. A. Hartman, J. K . Ruff, and J. A. Merritt, J . Amev. Chem. Soc., 90, 6329 (1968).
(15) H. UT. Iioesky, F. N. Tebbe, and E. L. Muetterties, Inorg. Chem., 9, 831 (1970). (16) I
