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A Low‐Spin Three‐Coordinate Cobalt(I) Complex and Its Reactivity toward H 2 and Silane
Author(s) -
Choi Jonghoon,
Lee Yunho
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201901007
Subject(s) - cobalt , chemistry , moiety , homolysis , steric effects , reactivity (psychology) , ligand (biochemistry) , crystallography , photochemistry , coordination sphere , pincer movement , electron paramagnetic resonance , stereochemistry , radical , inorganic chemistry , crystal structure , nuclear magnetic resonance , organic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , physics , pathology
A three‐coordinate low‐spin cobalt(I) complex generated using a pincer ligand is presented. Since an empty d x 2 - y 2orbital is sterically exposed at the site trans to the N donor of an acridane moiety, the cobalt(I) center accepts the coordination of various donors such as H 2 and PhSiH 3 revealing σ‐complex formation. At this low‐spin cobalt(I) site, homolysis of H–H and Si−H bonds preferentially occurs via bimolecular hydrogen atom transfer instead of two‐electron oxidative addition. When the resulting Co II –H species was exposed to N 2 , H 2 evolution readily occurs at ambient conditions. These results suggest single‐electron processes are favored at the structurally rigidified cobalt center.