Theoretical study of ammonia nucleophilic addition to nitriles in platinum complexes

The mechanism of the reaction of the ammonia nucleophilic addition to nitriles RC≡N, both free and activated in the platinum complex trans -[PtCl 2 (N≡CCH 3 ) 2 ], was studied in detail by theoretical quantumchemical methods. The reaction resulting in the formation of free or coordinated amidines pr...

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Bibliographic Details
Published in:Russian journal of general chemistry 2009-02, Vol.79 (2), p.232-241
Main Authors: Kuznetsov, M. L., Bokach, N. A., Kukushkin, V. Yu, Dement’ev, A. I.
Format: Article
Language:English
Subjects:
Chemistry
Chemistry and Materials Science
Chemistry/Food Science
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Summary:The mechanism of the reaction of the ammonia nucleophilic addition to nitriles RC≡N, both free and activated in the platinum complex trans -[PtCl 2 (N≡CCH 3 ) 2 ], was studied in detail by theoretical quantumchemical methods. The reaction resulting in the formation of free or coordinated amidines proceeds through consecutive formation of an orientation complex, a six-membered cyclic transition state, and a final reaction product, in which an amidine is in the E -configuration. Water containing in a solvent plays a role of a promoter of this process. The activation effect is interpreted from the viewpoint of both kinetic and thermodynamic factors. It was shown that the mechanism of the reaction product E-Z -isomerization includes the deprotonation of the amino-group nitrogen atom, the change of the coordinated ligand conformation, and the protonation of the nitrogen atom.
ISSN:1070-3632
1608-3350
DOI:10.1134/S107036320902011X