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

Article abstract of DOI:10.1016/j.ica.2003.06.013

The hydroxo complex [NBu₄]₂[Ni₂(C ₆F₅)₄(μ-OH)₂] reacts with ammonium O,σ-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 [NBu ₄][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 NiC ₂SO central cores, respectively.