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 C4 bridge are readily prepared from simple derivatisation reactions of the complex W(CCCCH)(CO)3Cp bearing the parent diynyl ligand. Complexes {Cp(OC)3W}CCCC{MLn} [MLn=M(CO)xCp (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CCCH)(CO)3Cp (1) with MXLn (X=halide) in NHEt2. Similarly, cis-PtCl2L2 (L=PEt3; L2=dppe, dppp) afforded cis-Pt{CCCC[W(CO)3Cp]}2L2. Lithiation of 1 (LiNPri2), followed by coupling with MnI(CO)5, gave {Cp(OC)3W}CCCC{Mn(CO)5}, while direct reaction of 1 with Hg(OAc)2 gave Hg{CCCC[W(CO)3Cp]}2. The Rh and Ir complexes react readily with O2 at the Group 9 metal centre; the crystal 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 are reported.