Some chemistry of diynyl-tungsten complexes

Abstract

Reactions between W(C≡CC≡CH)(CO)3Cp (1) and {Mo(CO)2Cp}2, Pt(η-C2H4)(PPh3)2 and 1,4-I2C6H4 [the latter catalysed by Pd0/Cu1] have given Mo2{μ-HC2C≡C[W(CO)3Cp]}(CO) 4Cp2 (2), Pt {η2-HC2C≡C[W(CO)3- Cp]}(PPh3)2 (3) and 1,4-{[W(CO)3Cp]C≡CC≡C}2C6H 4 (5), respectively. The adduct Co2{μ-PhC2C≡C[W(CO)3- Cp]}(μ-dppm)(CO)4 (6) was obtained from W(C≡CC≡CPh)(CO)3Cp (4) and Co2(μ-dppm)(CO)6. Substitution of one CO ligand in W(C≡CC≡CSiMe3)(CO)3Cp (7), prepared from the Cul-catalysed reaction of WCl(CO)3Cp with HC≡CC≡CSiMe3 in tetrahydrofuran/NHEt2, by bis(diphenylphosphino)methane/Me3NO gave W(C≡CC≡CSiMe3)(CO)2(dppm-P)Cp (8). Treatment of (7) with RuCl(PPh3)2Cp afforded {Cp(OC)3W}C≡CC≡C-{Ru(PPh3)2Cp} (9), which reacts at the W-C≡C- triple bond with tetracyanoethylene (tcne) to give {Cp(OC)3W}{C[=C(CN)2]C[=C(CN) 2]C≡C}{Ru(PPh3)2Cp} (10), and with Fe2(CO)9 to form the cluster Fe2W{μ3-C2C≡C[Ru(PPh 3)Cp]}(CO)8Cp (11).The molecular structures of (1), (2), (6), (8), (10) and (11) have been determined by single-crystal X-ray diffraction.