TY - JOUR
T1 - Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex
AU - Yang, Jindou
AU - Seo, Mi Sook
AU - Kim, Kyung Ha
AU - Lee, Yong Min
AU - Fukuzumi, Shunichi
AU - Shearer, Jason
AU - Nam, Wonwoo
N1 - Funding Information:
This work was supported by the NRF of Korea through CRI (NRF‐2012R1A3A2048842 to W.N.), Basic Science Research Program (2017R1D1A1B03029982 to Y.‐M.L., 2017R1D1A1B03032615 to S.F., and 2019R1I1A1A01055822 to M.S.S.) and the NSF of USA (CHE‐1900380 and CHE‐1854854 to J.S.). X‐ray absorption data were collected on beamline 07ID‐2 at the Canadian Light Source, which is supported by the CFI, NSERC, NRC, CIHR, the Government of Saskatchewan, and the University of Saskatchewan.
Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L., 2017R1D1A1B03032615 to S.F., and 2019R1I1A1A01055822 to M.S.S.) and the NSF of USA (CHE-1900380 and CHE-1854854 to J.S.). X-ray absorption data were collected on beamline 07ID-2 at the Canadian Light Source, which is supported by the CFI, NSERC, NRC, CIHR, the Government of Saskatchewan, and the University of Saskatchewan.
Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/8/3
Y1 - 2020/8/3
N2 - A mononuclear nonheme cobalt(III) iodosylbenzene complex, [CoIII(TQA)(OIPh)(OH)]2+ (1), is synthesized and characterized structurally and spectroscopically. While 1 is a sluggish oxidant in oxidation reactions, it becomes a competent oxidant in oxygen atom transfer reactions, such as olefin epoxidation, in the presence of a small amount of proton. More interestingly, 1 shows a nucleophilic reactivity in aldehyde deformylation reaction, demonstrating that 1 has an amphoteric reactivity. Another interesting observation is that 1 can be used as an oxygen atom donor in the generation of high-valent metal-oxo complexes. To our knowledge, we present the first crystal structure of a CoIII iodosylbenzene complex and the unprecedented reactivity of metal-iodosylarene adduct.
AB - A mononuclear nonheme cobalt(III) iodosylbenzene complex, [CoIII(TQA)(OIPh)(OH)]2+ (1), is synthesized and characterized structurally and spectroscopically. While 1 is a sluggish oxidant in oxidation reactions, it becomes a competent oxidant in oxygen atom transfer reactions, such as olefin epoxidation, in the presence of a small amount of proton. More interestingly, 1 shows a nucleophilic reactivity in aldehyde deformylation reaction, demonstrating that 1 has an amphoteric reactivity. Another interesting observation is that 1 can be used as an oxygen atom donor in the generation of high-valent metal-oxo complexes. To our knowledge, we present the first crystal structure of a CoIII iodosylbenzene complex and the unprecedented reactivity of metal-iodosylarene adduct.
KW - aldehyde deformylation reaction
KW - amphoteric reactivity
KW - cobalt(III) complexes
KW - iodosylbenzene adducts
KW - nonheme complexes
UR - http://www.scopus.com/inward/record.url?scp=85085555773&partnerID=8YFLogxK
U2 - 10.1002/anie.202005091
DO - 10.1002/anie.202005091
M3 - Article
C2 - 32358999
AN - SCOPUS:85085555773
SN - 1433-7851
VL - 59
SP - 13581
EP - 13585
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 32
ER -