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

The hydroxo complex [NBu4](2)[Ni-2(C6F5)(4)(mu-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), Pr-i (3)) and [NBu4][Ni(C6F5)(2){S(S)P(OR)Ar}] (Ar=p-MeOC6H4, R = Me (4), Et (5), Pr-i (6); Ar = ferrocenyl; R = Me (7), Et (8), Pr-i (9)). The monothiophosphonate nickel complexes [NBu4][Ni(C6F5)(2) {S(S)P(OR)(ferrocenyl))] (R=Et (10), Pr-i (11)) are obtained by reaction of the hydroxo complex with O-alkylferrocenyldithiophosphonate acids. Analytical (C, H, N, S), conductivity, and spectroscopic (IR, H-1, F-19 and P-31 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. (C) 2003 Elsevier B.V. All rights reserved.