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Theoretical study of acetonitrile‐exchange reactions on hexasolvated divalent cations in the first transition series elements
Author(s) -
Wasada Hiroaki,
WasadaTsutsui Yuko,
Hashimoto Tomohiro,
Funahashi Shigenobu
Publication year - 2009
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.22112
Subject(s) - chemistry , acetonitrile , transition state , computational chemistry , divalent , ab initio , cyanide , molecular orbital , crystallography , inorganic chemistry , molecule , organic chemistry , catalysis
Penta‐, hexa‐, and heptaacetonitrile complexes of divalent cations of the first transition series are studied by ab initio molecular orbital calculations. The factors that determine the structural stability and the reaction mechanism of solvent‐exchange reactions are discussed. All the penta‐ and hexaacetonitrile species are at local minima, whereas the geometrical stability of the heptacoordinated species depends on the 3 d electron configurations. The structural stability of heptaacetonitrile species is intermediate between those of hydrogen cyanide complexes and hydrates. Acetonitrile exchange reactions have more dissociative character than hydrogen cyanide exchange reactions because the inductive effect of the methyl group in CH 3 CN destabilizes the heptacoordinated structures. The successive binding energies show that associative mechanisms are favorable for acetonitrile exchange with earlier members of the first transition series, whereas dissociative mechanisms become favorable for later members. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009