In:
Bulletin of the Chemical Society of Japan, Oxford University Press (OUP), Vol. 71, No. 8 ( 1998-08-01), p. 1871-1886
Abstract:
Various optically active 1-substituted and 1,2-disubstituted ethyl cobaloxime [bis(dimethylglyoximato)cobalt(III)] complexes including deuterium-labeled complexes were prepared. Their photoracemization was found to occur upon irradiation of visible light in the solid-state. The reaction rate was much greater than that of solid-state racemization by irradiation of X-rays. The rates were not controlled by the electronic character of axial base and alkyl group but by the crystal lattice: the volume and shape of the reaction cavity, flexibility of the cavity, and intermolecular interaction such as hydrogen bonding. The experiments using deuterium-labeled complexes revealed the main reaction path in which the racemization proceeds mainly through out-of-plane rotation of the alkyl radical.
Type of Medium:
Online Resource
ISSN:
0009-2673
,
1348-0634
DOI:
10.1246/bcsj.71.1871
Language:
English
Publisher:
Oxford University Press (OUP)
Publication Date:
1998
detail.hit.zdb_id:
2041163-7
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