Organometallic nickel(II) complexes with dithiophosphate, dithiophosphonate and monothiophosphonate ligands

The hydroxo complex [NBu4]2[Ni2(C6F5)4(μ-OH)2] reacts with ammonium O,O′-dialkyldithiophosphates, O-alkyl-p-methoxyphenyldithiophosphonate acids and ammonium O-alkylferrocenyldithiophosphonates in dichloromethane under mild conditions to give, respectively, [NBu4][Ni(C6F5)2{S(S)P(OR)2}] (R=Me (1), Et (2), iPr (3)) and [NBu4][Ni(C6F5)2{S(S)P(OR)Ar}] (Ar=p-MeOC6H4, R=Me (4), Et (5), iPr (6); Ar=ferrocenyl; R=Me (7), Et (8), iPr (9)). The monothiophosphonate nickel complexes [NBu4][Ni(C6F5)2{S(S)P(OR)(ferrocenyl)}] (R=Et (10), iPr (11)) are obtained by reaction of the hydroxo complex with O-alkylferrocenyldithiophosphonate acids. Analytical (C, H, N, S), conductivity, and spectroscopic (IR, 1H, 19F and 31P NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of [NBu4][Ni(C6F5)2{S(S)P(OMe)(p-MeOC6H4)}] (4) and [NBu4][Ni(C6F5)2{S(O)P(OEt)(ferrocenyl)}] (10) shows that in both cases the coordination around the nickel atom es essentially square planar with NiC2S2 and NiC2SO central cores, respectively.