Mixed-metal cluster chemistry. 28. Core enlargement of tungsten-iridium clusters with alkynyl, ethyndiyl, and butadiyndiyl reagents

Gulliver T. Dalton, Lydie Viau, Susan M. Waterman, Mark G. Humphrey*, Michael I. Bruce, Paul J. Low, Rachel L. Roberts, Anthony C. Willis, George A. Koutsantonis, Brian W. Skelton, Allan H. White

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    12 Citations (Scopus)


    Reaction of [Wlr3(μ-CO)3(CO)8(η- C5Me5)] (1c) with [W(C=CPh)(CO)3(η-C5H5)] afforded the edge-bridged tetrahedral cluster [W2lr 342-C2Ph)(μ-CO)(CO) 9(η-C5H5)(η-C5Me 5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W 3lr342-C 2Ph)(μ-η2-C=CHPh)(CI)(CO)8(η-C 5Me5)(η-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C=CPh)(CO)3(η- C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a μ4η 2 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 W-W bond. Reaction of [Wlr3(CO)11(η-C5H5)] (1a) or 1c with [(η-C5H5)(CO)2Ru(C≡ C)Ru(CO)2(η-C5H5)] afforded [Ru 2Wlr352-C 2)(μ-CO)3(CO)7(η-C5H 5)2(η-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a Wlr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru - C scission, with insertion of the C2 unit into a W-lr bond of the cluster precursor. Reaction of [W 2lr2(CO)10(η-C5H 5)2] with the diruthenium ethyndiyl reagent gave [RuW 2lr242-(C 2C≡C)Ru(CO)2(η-C5H 5)}(μ-CO)2(CO)6(η-C5H 5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2lr2 unit capped by a Ru(η-C 5H5) group resulting from Ru - C scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W - Ir bond. Reaction between 1a, [Wlr3(CO) 11(η-C5H4Me)] (1b), or 1c and [η-C 5H5)(CO)3W(C≡CC≡C)W(CO) 3(η-C5H5)] afforded [W2lr 342-(C2C≡C)W(CO) 3(η-C5H5)}(μ-CO)2(CO) 2(η-C5H5)(η-C5R 5)] [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
    Number of pages9
    JournalInorganic Chemistry
    Issue number9
    Publication statusPublished - 2 May 2005


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