The structure of monomeric unsolvated and weakly solvated (Me2Cu)Li and (Me2Cu)Cu
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Density functional theory was used to study the structure of various isomers of (Me2Cu)Li (1), (Me2Cu)Cu (2), (Me2Cu)Li · 2Me2O (3), and (Me2Cu)Cu · 2Me2S (4) in the gas phase. Isomers of 1 and 3 were shown to be typical cuprates, whereas isomers of 2 and 4 should rather be treated as unsolvated and solvated methylcopper dimers, respectively. The reasons for the difference between structures 2, 4 and 1, 3 were considered. The energies of solvation of 1 by two dimethyl ether molecules (∼34 kcal/mol) and of 2 by two dimethyl sulfide molecules (∼36 kcal/mol) and the dissociation energies of all the compounds to the dimethylcuprate anion and the corresponding cation were calculated. The energies of solvation of 1 and 2 being almost equal, the transformation of 2 into 4 decreased the dissociation energy much more substantially than the transformation of 1 into 3.
KeywordsLithium Atom Valence Angle Bond Path Donor Acceptor Interaction Dihydrogen Bond
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