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Title: Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex
Abstract

A mononuclear nonheme cobalt(III) iodosylbenzene complex, [CoIII(TQA)(OIPh)(OH)]2+(1), is synthesized and characterized structurally and spectroscopically. While1is 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,1shows a nucleophilic reactivity in aldehyde deformylation reaction, demonstrating that1has an amphoteric reactivity. Another interesting observation is that1can 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 CoIIIiodosylbenzene complex and the unprecedented reactivity of metal‐iodosylarene adduct.

 
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NSF-PAR ID:
10156267
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie
Volume:
132
Issue:
32
ISSN:
0044-8249
Page Range / eLocation ID:
p. 13683-13687
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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    A mononuclear nonheme cobalt(III) iodosylbenzene complex, [CoIII(TQA)(OIPh)(OH)]2+(1), is synthesized and characterized structurally and spectroscopically. While1is 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,1shows a nucleophilic reactivity in aldehyde deformylation reaction, demonstrating that1has an amphoteric reactivity. Another interesting observation is that1can 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 CoIIIiodosylbenzene complex and the unprecedented reactivity of metal‐iodosylarene adduct.

     
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