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

doi:10.1021/acs.organomet.0c00772

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

Department of Fundamental Organic Chemistry

Research output: Contribution to journal › Article › peer-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 language	English
Journal	Organometallics
DOIs	https://doi.org/10.1021/acs.organomet.0c00772
Publication status	Accepted/In press - 2021

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{fda8f74abfbd45feb15a44252352c100,

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

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. ",

author = "Hideki Sugimoto and Kurumi Aoki and Mayuko Miyanishi and Yoshihito Shiota and Kazunari Yoshizawa and Shinobu Itoh",

note = "Funding Information: This work was supported by KAKENHI (Grant-in-Aid) for Scientific Research (No. 19K05497) and by JST-CREST (JPMJCR16P1). ",

year = "2021",

doi = "10.1021/acs.organomet.0c00772",

language = "English",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

}

TY - JOUR

T1 - Oxygen Atom Insertion into the Osmium-Carbon Bond via an Organometallic Oxido-Osmium(V) Intermediate

AU - Sugimoto, Hideki

AU - Aoki, Kurumi

AU - Miyanishi, Mayuko

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Itoh, Shinobu

N1 - Funding Information: This work was supported by KAKENHI (Grant-in-Aid) for Scientific Research (No. 19K05497) and by JST-CREST (JPMJCR16P1).

PY - 2021

Y1 - 2021

N2 - 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.

AB - 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.

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