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Identifying similarities and differences between analogous bisdithiolene and bisdiselenolene complexes: A computational study
Author(s) -
Bushnell Eric A. C.,
Boyd Russell J.
Publication year - 2016
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25044
Subject(s) - chalcogen , chemistry , reactivity (psychology) , sulfur , selenium , ligand (biochemistry) , electron transfer , metal , atom (system on chip) , substitution (logic) , computational chemistry , kinetic energy , redox , crystallography , inorganic chemistry , organic chemistry , medicine , biochemistry , physics , alternative medicine , receptor , pathology , quantum mechanics , computer science , embedded system , programming language
Due to ligand non‐innocence and reversible one‐electron‐transfer processes dithiolene complexes have been intensively studied both experimentally and computationally. While the substitution of the ligating sulfur atoms by selenium provides a means to delicately tune the behavior of dithiolene compounds, diselenolene complexes have not been as thoroughly examined. Yet, the search for such ligands has been ongoing since the 1970s. Thus, we have looked at several metal‐bisdiselenolene complexes and have compared key properties of these complexes with their bisdithiolene analogues to determine the effect of substituting the chalcogen atom. The results herein show that substitution of the sulfur atoms by selenium within these complexes only subtly changes the thermodynamics and kinetic reactivity of bisdithiolene complexes while not significantly affecting the geometries of the complexes. The significance being that the relatively minor structural changes that occur upon redox is a key feature of dithiolene complexes. Due to ligand non‐innocence and reversible one‐electron‐transfer processes dithiolene complexes have been intensively studied, however, diselenolene complexes have not. First‐principles calculations show that substitution of the sulfur atoms by selenium within the investigated complexes does offer the ability to subtly tune the thermodynamics and kinetic reactivity of bisdithiolene complexes, while not significantly affecting the geometries of the complexes. © 2015 Wiley Periodicals, Inc.