Preparation, structures and some reactions of novel diynyl complexes of iron and ruthenium

Abstract

Reactions between HCCCCSiMe₃ and several ruthenium halide precursors have given the complexes Ru(CCCCSiMe₃)(L₂)Cp′ [Cp′ = Cp, L = CO (1), PPh₃ (2); Cp′ = Cp*, L₂ = dppe (3)]. Proto-desilylation of 2 and 3 have given unsubstituted buta-1,3-diyn-1-yl complexes Ru(CCCCH)(L₂)Cp′ [Cp′ = Cp, L = PPh₃ (5); Cp′ = Cp*, L₂ = dppe (6)]. Replacement of H in 5 or 6 with Au(PR₃) groups was achieved in reactions with AuCl(PR₃) in the presence of KN(SiMe₃)₂ to give Ru(CCCCAu(PR₃)}(L₂)Cp′ [Cp′ = Cp, L = PPh₃, R = Ph (7); Cp′ = Cp*, L₂ = dppe, R = Ph (8), tol (9)]. The asymmetrically end-capped {Cp(Ph₃P)₂Ru}CCCC{Ru(dppe)Cp*} (10) was obtained from Ru(CCCCH)(dppe)Cp* and RuCl(PPh₃)₂Cp. Single-crystal X-ray structural determinations of 1–3 and 6–9 are reported, with a comparative determination of the structure of Fe(CCCCSiMe₃)(dppe)Cp* (4), and those of a fifth polymorph of {Ru(PPh₃)₂Cp}₂(μ-CCCC) (12), and {Ru(dppe)Cp}₂(μ-CCCC) (13).