Oxygen Atom Insertion into the Osmium-Carbon Bond via an Organometallic Oxido-Osmium(V) Intermediate

Hideki Sugimoto, Kurumi Aoki, Mayuko Miyanishi, Yoshihito Shiota, Kazunari Yoshizawa, Shinobu Itoh

Research output: Contribution to journalArticlepeer-review

Abstract

A cyclometalated osmium(III) complex, [OsIIICl(phpy)(tpy)]+ (OsIII(phpy); phpy = 2-C6H4-2′-C5H4N-κC,N) is synthesized from OsIIICl3(tpy) (tpy = 2,2′6′,2″-terpyridine) and 2-phenylpyridine (H-phpy) in the presence of AgPF6, in which the metalated carbon atom is disposed trans to the chlorido ligand. Oxidation of OsIII(phpy) with oxygen atom transfer oxidants such as N-methylmorpholine N-oxide (NMO), N,N-dimethylaniline N-oxide (DMAO), H2O2, t-BuOOH, and m-chloroperoxybenzoic acid (m-CPBA) in CH3CN or electron transfer type oxidants such as (NH4)2S2O8 and ammonium hexanitratocerate (CAN) in H2O/acetone causes oxygen atom insertion between the osmium(III)-carbon bond to give a phenoxido-osmium(III) complex OsIII(O-phpy). Isotope labeling experiments using H218O and kinetic studies as well as calculation studies indicate formation of an organometallic oxido-osmium(V) complex as the active intermediate.

Original languageEnglish
JournalOrganometallics
DOIs
Publication statusAccepted/In press - 2021

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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