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The Mechanism of Hydroamination of Allenes, Alkynes, and Alkenes Catalyzed by Cyclopentadienyltitanium–Imido Complexes: A Density Functional Study
Author(s) -
Straub Bernd F.,
Bergman Robert G.
Publication year - 2001
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/1521-3773(20011217)40:24<4632::aid-anie4632>3.0.co;2-v
Subject(s) - hydroamination , library science , chemistry , citation , computer science , catalysis , organic chemistry
Proton transfer from ammine or amide ligands to vinylamine‐type π systems in intermediary titanacycles (see picture) of allene and alkyne hydroamination reactions is predicted by DFT model calculations. The weaker coordination of alkenes to the Ti=N fragment, the lack of a π system in the titanacycle, and thus the necessity of direct Ti−C bond protonation rationalize a higher barrier for alkene hydroamination.