Oxygen Atom Insertion into the Osmium–Carbon Bond via an Organometallic Oxido–Osmium(V) Intermediate
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https://figshare.com/articles/dataset/Oxygen_Atom_Insertion_into_the_Osmium_Carbon_Bond_via_an_Organometallic_Oxido_Osmium_V_Intermediate/13548004
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资源简介：
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.
创建时间：
2021-01-08
