Mixed-Metal Cluster Chemistry. 28. Core Enlargement of Tungsten-Iridium Custers with Alkynyl, Ethyndiyl and Butadiyndiyl Reagents

G.T. Dalton, L. Viau, S.M. Waterman, M.G. Humphrey, M.I. Bruce, P.J. Low, R.L. Roberts, A.C. Willis, George Koutsantonis, Brian Skelton, Allan White

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Reaction of [WIr3(μ-CO)3(CO)8(η-C5Me5)] (1c) with [W(CCPh)(CO)3(η-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(μ4-η2-C2Ph)(μ-CO)(CO)9(η-C5H5)(η-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(μ4-η2-C2Ph)(μ-η2-CCHPh)(Cl)(CO)8(η-C5Me5)(η-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(CCPh)(CO)3(η-C5H5)] into IrIr and WIr bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a μ4-η2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a μ4-η2 fashion, as well as a vinylidene ligand bridging a WW bond. Reaction of [WIr3(CO)11(η-C5H5)] (1a) or 1c with [(η-C5H5)(CO)2Ru(CC)Ru(CO)2(η-C5H5)] afforded [Ru2WIr3(μ5-η2-C2)(μ-CO)3(CO)7(η-C5H5)2(η-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone RuC scission, with insertion of the C2 unit into a WIr bond of the cluster precursor. Reaction of [W2Ir2(CO)10(η-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{μ4-η2-(C2CC)Ru(CO)2(η-C5H5)}(μ-CO)2(CO)6(η-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(η-C5H5) group resulting from RuC scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the WIr bond. Reaction between 1a, [WIr3(CO)11(η-C5H4Me)] (1b), or 1c and [(η-C5H5)(CO)3W(CCCC)W(CO)3(η-C5H5)] afforded [W2Ir3{μ4-η2-(C2CC)W(CO)3(η-C5H5)}(μ-CO)2(CO)2(η-C5H5)(η-C5R5)] [R = H (7a), Me (7c); R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.
Original languageEnglish
Pages (from-to)3261-3269
JournalInorganic Chemistry
Volume44
Issue number9
DOIs
Publication statusPublished - 2005

Fingerprint Dive into the research topics of 'Mixed-Metal Cluster Chemistry. 28. Core Enlargement of Tungsten-Iridium Custers with Alkynyl, Ethyndiyl and Butadiyndiyl Reagents'. Together they form a unique fingerprint.

Cite this