Thiobenzoato complexes

Only the green crystals of the chromium tris(thiobenzoato) complex Cr(PhCOS)3 21 have been obtained, by the stoichiometric reaction of CrCl3 6H20 with sodium thiobenzoate in aqueous conditions [73,271]. Like many other Cr(III) complexes, the complex 21 is a monomer in which the three thiobenzoato ligands bind to the metal in chelate mode. 

It is well-known that the reaction of palladium(II) acetate with an excess of thiobenzoic acid in benzene gives the polymeric thiobenzoato palladium complex 51 [Pd(PhCOS)2]x (x>3) [83], although the complex formed from the reaction of PdCl2 with sodium thiobenzoate in water was reported to be dimeric [Pd(PhCOS)2]2 in benzene [253]. The thiobenzoato complexes 51 obtained by the reaction of Na2PdCl4 with sodium thiobenzoate react with Lewis bases to give the neutral monomeric complexes trans-Pd(PhCOS)2(L)2 (L R P, R3AS, RsSb, pyridines, and so on), where the PhCOS ligands are monodentate... 

Bis(thiocarboxylato) niobium 18Nb(RCOS)2 [207] and bis(r] -cyclopenta-di-enyl)bis(thiobenzoato)niobium 19 [110] have been synthesized by stoichiometric reactions of NbCl2 with sodium thiocarboxylates and of Nb(Cp)2X2 (X=C1, Br, I) with thallium thiobenzoate, respectively. The structure of 19 is considered to be analogous to the tantalum complex 20, in which the thiocar-boxylato ligands are monodentate through the sulfur atom [110]. 

The reaction of Re(CO)5Br with PhCOSH gives the dimeric complex 30, where the thiocarboxyl sulfur atom is coordinated to the two rhenium atoms [99], whereas heating with cesium thiobenzoate in ethanol leads to the anion complexes 31 in which the S-thiobenzoato ligands are triply bridged to the two rhenium atoms [213]. In addition, reaction with Cs2(SOC-COS) affords (OC)5Re(SOC-COS)Re(CO)5 [326], the structure of which resembles that of the corresponding manganese complex 28. 

Only one osmium complex 40 with a thiobenzoato ligand has been synthesized, by the reaction of Os3(CO)io(CH3CN)2 with thiobenzoic acid [2]. The thiobenzoato ligand is bound to the metal in the ju,/] -mode through the... 

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