Reaction of polynuclear acetylide clusters. Synthesis of pentanuclear heterometallic clusters by addition of [m(CO)3(C≡CPh)(η-C5H5)] to [mOs3(CO)11(C≡CPh)(η-C5H 5)] (M = Mo or W). Crystal structures of [mo2...
Journal
Journal of the Chemical Society, Dalton Transactions
Journal Issue
10
Pages
3025-3031
Date Issued
1990
Author(s)
Abstract
Title full:Reaction of polynuclear acetylide clusters. Synthesis of pentanuclear heterometallic clusters by addition of [m(CO)3(C≡CPh)(η-C5H5)] to [mOs3(CO)11(C≡CPh)(η-C5H 5)] (M = Mo or W). Crystal structures of [mo2Os3(CO)11(CCPhCCPh)(η-C 5H5)2]·2H2O. Both the cluster acetylide complexes [MOs3(CO)11(C≡CPh)(η-C5H 5)] [M = Mo, (1); or W, (2)] react with [Mo(CO)3(C≡CPh)(η-C5H5)] to give in low yield planar pentanuclear complexes [MMoOs3(CO)11(CCPhCCPh)(η-C5H 5)2] [M = Mo, (3); or W, (4)] which contain a C4 hydrocarbon fragment derived from head-to-tail coupling between the two acetylide fragments. The C4 chain of these complexes also undergoes twisting in solution, indicated by variable-temperature 1H n.m.r. studies. Reaction of complex (1) with [W(CO)3(C≡CPh)(η-C5H5)] does not produce the coupling product but induces C-C bond scission of [W(CO)3(C≡CPh)(η-C5H5)] giving a novel carbide-alkylidyne complex [MoWOs3(CO)8(μ4-C)(μ 3-CPh)(CCPh)(η-C5H5)2] (5) in low yield. The structures of complexes (3) and (5) have been determined by single-crystal X-ray diffraction studies. Crystal data for (3): space group P21/n, a = 9.583(3), b = 25.175(10), c = 16.300(7) Å, β = 91.26(3)°, Z = 4, R = 0.051, and R′ = 0.053. Crystal data for (5): space group P1, a = 10.072(6), b = 13.217(3), c = 14.800(3) Å, α = 95.41(2), β = 93.17(4), γ = 109.14(4)°, Z = 2, R = 0.056, and R′ = 0.062.
SDGs
Type
journal article