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Asymmetric hydrogenation with iridium C,N and N,P ligand complexes : characterization of dihydride intermediates with a coordinated alkene

Gruber, Stefan and Pfaltz, Andreas. (2014) Asymmetric hydrogenation with iridium C,N and N,P ligand complexes : characterization of dihydride intermediates with a coordinated alkene. Angewandte Chemie International Edition, 53 (7). pp. 1896-1900.

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Official URL: http://edoc.unibas.ch/dok/A6337607

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Abstract

Previously elusive iridium dihydride alkene complexes have been identified and characterized by NMR spectroscopy in solution. Reactivity studies demonstrated that these complexes are catalytically competent intermediates. Additional H2 is required to convert the catalyst-bound alkene into the hydrogenation product, supporting an Ir(III) /Ir(V) cycle via an [Ir(III) (H)2 (alkene)(H2 )(L)](+) intermediate, as originally proposed based on DFT calculations. NMR analyses indicate a reaction pathway proceeding through rapidly equilibrating isomeric dihydride alkene intermediates with a subsequent slow enantioselectivity-determining step. As in the classical example of asymmetric hydrogenation with rhodium diphosphine catalysts, it is a minor, less stable intermediate that is converted into the major product enantiomer.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Synthetische organische Chemie (Pfaltz)
UniBasel Contributors:Pfaltz, Andreas
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Wiley
ISSN:1433-7851
e-ISSN:1521-3773
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:10 Apr 2017 08:40
Deposited On:06 Feb 2015 09:59

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