New Mechanism for the Intermolecular Hydroamination of Alkynes:  Catalysis by Dinuclear Ruthenium Complexes with a Rigid Dicyclopentadienyl Ligand

The dinuclear ruthenium complex {(η5-C5H3)2(SiMe2)2}Ru2(CO)3(C2H4)H+BF4 - (1) catalyzes the intermolecular hydroamination of arylalkynes (e.g., phenylacetylene) with arylamines (e.g., p-toluidine) to give imines (e.g., (Ph(Me)CN(p-MeC6H4)). Although the catalyst has a limited lifetime (up to 6 turn...

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Bibliographic Details
Published in:Organometallics 2004-11, Vol.23 (24), p.5662-5670
Main Authors: Klein, David P, Ellern, Arkady, Angelici, Robert J
Format: Article
Language:English
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Summary:The dinuclear ruthenium complex {(η5-C5H3)2(SiMe2)2}Ru2(CO)3(C2H4)H+BF4 - (1) catalyzes the intermolecular hydroamination of arylalkynes (e.g., phenylacetylene) with arylamines (e.g., p-toluidine) to give imines (e.g., (Ph(Me)CN(p-MeC6H4)). Although the catalyst has a limited lifetime (up to 6 turnovers), details of the reaction mechanism have been elucidated by isolation and characterization (X-ray and/or NMR) of six of the seven intermediates and reaction-terminating species. The mechanism is fundamentally different from all previously proposed mechanisms for alkyne hydroamination. The rigid doubly bridged bis((dimethylsilyl)cyclopentadienyl) ligand is an important feature of the catalyst that facilitates this new type of hydroamination mechanism.
ISSN:0276-7333
1520-6041
DOI:10.1021/om049377u