Instability of metal 1,3-benzodi(thiophosphinoyl)methandiide complexes: formation of hafnium, tin and zirconium complexes of 1,3-benzodi(thiophosphinoyl)thioketone dianionic ligand [1,3-C6H4(PhPS)2CS]2−.

The reaction of [LCH2] (1, L = 1,3-C6H4(PhPS)2) and M(NMe2)4 (M = Hf, Zr) in toluene at 110 °C afforded a mixture of group 4 metal complexes [{LC(S)}2M] [M = Hf (2), Zr (3)] and [1,3-C6H4(PhPS)(PhP)CH2]. The reactions appear to proceed through the formation of metal bis(carbene) complexes, [LC=M=CL], which then undergo an intermolecular sulphur transfer reaction with the P=S bond of [LCH2] to form 2 and 3, and the byproduct is [1,3-C6H4(PhPS)(PhP)CH2]. In addition, the reaction of 1, [CH2(PPh2S)2] (4) and M(NMe2)4 in refluxing toluene gave a mixture of [{LC(S)}M(NHMe2){C(PPh2S)2}] [M = Hf (5), Zr (6)], [1,3-C6H4(PhPS)(PhP)CH2] and [CH2(PPh2S)(PPh2)]. Moreover, the intermolecular sulfur transfer reaction is evidenced by the reaction of the tin(ii) 1,3-benzodi(thiophosphinoyl)methandiide complex [{μ-1,3-C6H4(PhPS)2C}Sn]2 (7) with two equivalents of elemental sulfur in CH2Cl2 at ambient temperature to give [{1,3-C6H4(PhPS)2CS}2Sn] (8). Compounds 2, 3, 5, 6, and 8 were characterized by NMR spectroscopy and X-ray crystallography. [ABSTRACT FROM AUTHOR]