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Spontaneous Bicyclometalation of a Single Cobalt(I) Complex Stabilized by a δ‐C–H Agostic Interaction
Author(s) -
Beck Robert,
Camadanli Sebnem,
Klein HansFriedrich
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201701221
Subject(s) - agostic interaction , chemistry , metalation , cobalt , ring (chemistry) , coordination sphere , chelation , density functional theory , ligand (biochemistry) , crystallography , stereochemistry , reactivity (psychology) , computational chemistry , metal , inorganic chemistry , crystal structure , organic chemistry , pathology , medicine , biochemistry , receptor , alternative medicine
CoCH 3 (PMe 3 ) 4 is known for a long time for its potential to activate less reactive C–H Bonds under extremely mild conditions by methane elimination. A spontaneous second C–H bond activation at the same center of cobalt complex is not expected. In contrast to previous investigations with certain aryl‐iminophosphane chelating ligands, in this work two consecutive metalation steps at the same complex center lead to a rare example of a cobalt metallabicycle. In the first step a C–H activation results in a five‐membered chelate ring, whereas the second ring is formed by an incomplete C–H activation which stops at a stable, rarely observed δ‐C–H agostic interaction. The results are supported by NMR spectroscopy, X ray structure analysis and density functional theory (DFT) calculations. Knowledge of such agostic interactions are essential in order to understand catalytic reaction paths and studies of such molecular structures of their ring sizes, bite angles and electronic properties have shown that these ligands allow sensitive control within the metal coordination sphere.

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