Heterometallic complexes containing C4 chains.: X-ray structures of {Cp(OC)3W}C≡CC≡C{Ir(CO)(PPh3)2(O2)} and cis-Pt{C≡CC≡C[W(CO)3Cp]}2(PEt3)2

Heterometallic diyndiyl complexes containing tungsten linked to metals of Groups 6-12 through a C, bridge are readily prepared from simple derivatisation reactions of the complex W(C equivalent to CC equivalent to CH)(CO)(3)Cp bearing the parent diynyl ligand. Complexes {Cp(OC),W} C equivalent to CC equivalent to C {MLn} [MLn = M(CO)(x) Cp (n = 3, M = Mo, W; n = 2, M = Fe, Ru), M(CO)(PPh3)(2) (M = Rh, Ir), Au(PPh3)] have been obtained from CuI-catalysed reactions of W(C equivalent to CC equivalent to CH)(CO)(3)Cp (1) with MXLn (X = halide) in NHEt2. Similarly, cis-PtCl2L2 (L = PEt3; L-2 = dppe, dppp) afforded cis-Pt{C equivalent to CC equivalent to C[W(CO)(3)Cp]}(2)L-2. Lithiation of 1 (LiNPr2i), followed by coupling with MnI(CO)(5), gave {Cp(OC)(3)W}C equivalent to CC equivalent to C{Mn(CO)(5)}, while direct reaction of 1 with Hg(OAc)(2) gave Hg{C equivalent to CC equivalent to C[W(CO)(3)Cp]}(2). The Rh and Ir complexes react readily with O-2 at the Group 9 metal centre; the crystal structures of {Cp(OC)(3)W}C equivalent to CC equivalent to C{Ir(CO)(PPh3)(2)(O-2)} and cis-Pt{C equivalent to CC equivalent to C[W(CO)(3)Cp]}(2)(PEt3)(2) are reported. (C) 2000 Elsevier Science S.A. All rights reserved.