Mixed-metal cluster chemistry. 31.(1) reactions of dimolybdenum-diiridium clusters with alkylidyne complexes

Michael D. Randles, Rian D. Dewhurst, Marie P. Cifuentes*, Mark G. Humphrey

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    11 Citations (Scopus)

    Abstract

    Reactions of the tetrahedral clusters Mo 2Ir 2(μ-CO) 3(CO) 75-L) 2 (L = C 5H 5, C 5HMe 4) with the molybdenum alkylidyne complex Mo(≡CC 6H 4OMe-4)(CO) 2{(N 2C 3H 3) 3BH- κ 3N,N′,N″} afford the pentanuclear clusters Mo 3Ir 24-C)(μ 3-CC 6H 4OMe-4)(μ-O)(CO) 6{(N 2C 3H 3) 3BH-κ 3N,N′,N″} (η 5-C 5H 5) 2 (1; 62%) and Mo 3Ir 23-CC 6H 4OMe-4) (μ 32-CO)(μ-CO)(CO) 6{(N 2C 3H 3) 3BH-κ 3N, N′,N″}(η 5-C 5Me 4H) 2 (2; 65%), respectively, while the reaction of Mo 2Ir 2(μ-CO) 3(CO) 7(η-C 5H 5) 2 with W(≡CC≡CSiMe 3)(CO) 2{(N 2C 3H 3) 3BH- κ 3N,N′,N″} yields the butterfly cluster Mo 2Ir 242-SiMe 3C 2C≡W(CO) 2{(N 2C 3H 3) 3BH-κ 3N,N′,N″} )(μ-CO) 4(CO) 45-C 5H 5) 2 (3; 60%). The identities of 1-3 have been confirmed by single-crystal X-ray diffraction studies. Cluster 1 contains μ 4-carbido and μ-oxido ligands resulting from CO cleavage. Cluster 2, with sterically more encumbering tetramethylcyclopentadienyl ligands that arrest CO cleavage, possesses a μ 32-CO ligand with a weak CO bond (1.272(7), 1.257(7) Å). Cluster 2 could not be converted into an analogue of cluster 1. The reaction with alkyne is more facile than the reaction with alkylidyne; cluster 3 results from addition of the C≡C bond (rather than the W≡C bond) across the Mo-Mo vector.

    Original languageEnglish
    Pages (from-to)2582-2588
    Number of pages7
    JournalOrganometallics
    Volume31
    Issue number7
    DOIs
    Publication statusPublished - 9 Apr 2012

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