Osmium(II)-Induced Rearrangement of Allenols for Metallafuran Complexes

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

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Author(s)

  • King-Ting Tam
  • Shek-Man Yiu
  • Man-Kit Tse
  • Robert H. Morris

Detail(s)

Original languageEnglish
Pages (from-to)1931–1941
Journal / PublicationOrganometallics
Volume41
Issue number15
Online published11 Jul 2022
Publication statusPublished - 8 Aug 2022

Abstract

Osmafuran complexes in the form of cis-[Os(L∧L)2(C∧O)]+ (L∧L = 1,1-bis(diphenylphosphino)methane (dppm) or 2,2'-bipyridine (bpy); C∧O = [C(CH3)C(CH3)CRO]-, coordinating atoms in italics) were prepared from reactions between dichloro-Os(II) complexes cis-[Os(L∧L)2Cl2] and allenols H2C=C=C(CH3)(CH(R)(OH)) in alcoholic solvents. Rearrangement of allenolates H2C=C=C(CH3)(CH(R)(O-)) involving deprotonation of the secondary alcoholic carbon and protonation of the terminal allenic carbon was evident from the X-ray crystal structures of the resulting complexes. Density functional theory (DFT) calculations suggested a rearrangement mechanism involving Os-alkene intermediates cis-[Os(L∧L)2(H2C=CH-C(CH3)(=C(R)(O-)))]+ but not Os-hydride intermediates. Overall, these osmafurans are not directly derived from common metal-allene reaction patterns.

Research Area(s)

  • METAL-CATALYZED REACTIONS, INSERTION REACTIONS, BOND ACTIVATION, CHEMISTRY, OSMIUM, CYCLIZATION, VINYLIDENE, OSMACYCLES, REACTIVITY, ALKYNES

Citation Format(s)

Osmium(II)-Induced Rearrangement of Allenols for Metallafuran Complexes. / Shek, Hau-Lam; Tam, King-Ting; Yiu, Shek-Man et al.
In: Organometallics, Vol. 41, No. 15, 08.08.2022, p. 1931–1941.

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review