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Metallaoxetanes and Carbenes from Diolates in High‐Valent Rhenium Oxo Chemistry: The Importance of the Coordination Number
Author(s) -
Chen Xueyi,
Zhang Xiangyang,
Chen Peter
Publication year - 2003
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200351496
Subject(s) - rhenium , carbene , chemistry , reactivity (psychology) , coordination complex , cleave , stereochemistry , computational chemistry , organic chemistry , catalysis , metal , medicine , alternative medicine , pathology , enzyme
Re V diolate complexes cleave to form either the Re VII trioxo complex or a rhenium carbene, depending on the coordination number of the original diolate complex (see picture). The carbene complexes, detected by using collision induced mass spectrometry, are the best experimental indication to date for intermediate “metallaoxetanes”, which would be the first‐formed intermediate in [2+2] reactions of olefins with a d 0 oxo complex. This sharp dichotomy in reactivity can be explained by a qualitative π‐strain model.