American Chemical Society
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Comparison of the Reactivity of M(allyl)3 (M = Rh, Ir) with Donor Ligands

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journal contribution
posted on 2000-12-16, 00:00 authored by Kevin D. John, Kenneth V. Salazar, Brian L. Scott, R. Thomas Baker, Alfred P. Sattelberger
Reactions of M(allyl)3 [M = Rh, Ir] with a variety of donor ligands have been investigated. While both complexes are unreactive toward “hard” N- and O-donor ligands, “soft” ligands such as tolylisothiocyanate, tertiary phosphines, CO, and aryl isocyanides are readily added. Whereas ligand additions to Rh(allyl)3 are often accompanied by reduction of the Rh(III) center, analogous reactions with Ir(allyl)3 afford stable trivalent products containing σ-allyl ligands. The molecular structures of several derivatives are presented, including Ir(σ-allyl)(π-allyl)2(PPh3), Ir(σ-allyl)2(π-allyl)(PMe3)2, and Ir(σ-allyl)3(C⋮N-2,6-Me2C6H3)3.