Vanadium complexes dithiophosphinates

Oxovanadium(IV) complexes with dithiophosphate ligands have been extensively examined <8,121.161,252,386) x typical ESR spectrum is shown in Fig. 7. In addition to the eight vanadium 1=112 hyperfine lines phosphorus (/ = 1/2) superhyperfine splitting is also observed. The phosphorus superhyper-fine splitting can be considered a bit unusual since the phosphorus is located about 3 A or more away from the metal ion. P and As superhyperfine splitting has been observed in the ESR spectra of ill-defined vanadium phosphine 388) and arsine 389) complexes but in those cases, presumably, direct V-P and V—As interactions occur. ESR parameters have been tabulated for a large number of dithiophosphate 121,252) dithiophosphinate 121.252) complexes. Evaluation 3i) of the fractional 3s character of unpaired electron in dithiophosphate complexes yielded a value of 1.35%. The vanadyl(IV) complexes possess approximate C2V symmetry. The unpaired d electron resides... 

Dithiophosphinate complexes [V(S2PX2)3] (X = F, CF3, Me, Ph, OEt) were reported293 and the structure where X = OEt has been determined.294 The six sulfur atoms form a trigonally distorted octahedron around vanadium with the average V—S distance 2.45 0.02 A. Visible spectra (in CH2C12 or an oriented crystal) show four bands a charge-transfer band is observed at 22700 and 23 300 cm-1 in the solution and crystal. The others at 12 820, 18080 and 26 400 cm-1 (13 200, 18 400 and 26 400 in the crystal) are the expected transitions for octahedral V111. 

Vanadium(III) complexes, 473 adenine, 475 alcohols, 478 amides, 474, 480 amines, 474 amino acids, 484 ammonia, 474 aqua, 477 arsines, 476 azide, 475 bipyridyl, 475 bromides, 483 carboxylates, 479 catecholates, 478 chlorides, 482 complexones, 485 cyanides, 474,476 (Wethyl sulfoxide, 480 dioxygen, 478 dithiocarbamates, 481 dithiolates, 481 dithiophosphinates, 481 ethers, 478... 

A vanadium(iii) complex of bis(trifluoromethyl)dithiophosphinic acid can be prepared by the reaction of an excess of the acid with vanadium trichloride under anhydrous oxygen-free conditions with VjOs or VOCIj, mixtures of the vanadiumOii) and vanadyl complexes V SjPCCFJs s and VO SgPfCFs), >2 are obtained, and can be separated by fractional sublimation. The magnetic properties and infrared and electronic spectra of the V complex are compared with those of other substituted dithiophosphinates. 

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