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Electron Transfer Induced CS Bond Cleavage in Rhenium and Technetium Thioether Complexes: Structural and Chemical Evidence for π Back‐Donation to CS σ * Orbitals
Author(s) -
Mullen Gregory E. D.,
Went Michael J.,
Wocadlo Sigrid,
Powell Anne K.,
Blower Philip J.
Publication year - 1997
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199712051
Subject(s) - rhenium , thioether , atomic orbital , chemistry , osmium , cleavage (geology) , electron transfer , bond cleavage , metal , molecular orbital , chemical bond , sulfur , crystallography , electron , photochemistry , materials science , inorganic chemistry , stereochemistry , molecule , organic chemistry , physics , catalysis , composite material , quantum mechanics , fracture (geology) , ruthenium
The trends in carbon‐sulfur bond length for complexes of 1,4,7‐trithiacyclononane (9S3) provide compelling evidence that CS σ * orbitals accept π‐electron density from the metal. As the metal d‐orbital energy and occupancy increase, this leads ultimately to cleavage of the CS bonds with concomitant release of ethene in the Re and Tc complexes [Eq. (a)].