Actions for Electropholic Transition Metal Complexes [electronic resource] : Catalysis of Isotope Exchange. April 1, 1992 - December 3, 1996. Final Report

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Electropholic Transition Metal Complexes [electronic resource] : Catalysis of Isotope Exchange. April 1, 1992 - December 3, 1996. Final Report

Published
Washington, D.C. : United States. Dept. of Energy. Office of Energy Research, 1997.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Physical Description
3 pages : digital, PDF file
Additional Creators
United States. Department of Energy. Office of Energy Research and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
The central aim of this project is to exploit transition metal dihydrogen complexes to develop catalysts for isotope exchange reactions between hydrogen and substrates such as water. The authors have partially met this goal by the synthesis of novel cationic rhenium complexes of the form [Re(CO)₃(PR₃)₂(H₂)]⁺. These complexes bind hydrogen somehwat more strongly than the neutral tungsten analogs but also activate the bound H₂ to heterolytic cleavage. Thus rapid proton (deuteron) exchange between hydrogen and water can be achieved. An example of this reaction is the rapid formation of bound HD from the complex [Re(CO)₃(PR₃)₂(H₂)]⁺ and deuterium gas. Rapid incorporation of deuterium from D₂O has also been observed. In these systems, the competitive binding of water to the metal center is a drawback. The affinity of the Re center for water depends upon the nature of the phosphine ligands, with the presumably more electrophilic PPh₃ complex binding water strongly and irreversibly, while the PCy₃ complex binds water reversibly. These results have been published in J.Am.Chem.Soc 1994, 116, 4515 and J.Am.Chem.Soc 1997, 119, 4172.
Report Numbers
E 1.99:755548
Subject(s)
Other Subject(s)
Note
Published through SciTech Connect.
04/06/1997.
Heinekey, D. Michael.
Univ. of Washington, Seattle, WA (US)
Type of Report and Period Covered Note
Final; 04/01/1992 - 12/03/1996
Funding Information
FG06-92ER14254
View MARC record | catkey: 14394013