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J Am Chem Soc. 2009 Dec 9;131(48):17552-3. doi: 10.1021/ja908644n.

Highly stereoselective proton/hydride exchange: assistance of hydrogen bonding for the heterolytic splitting of H2.

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1
Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching b. München, Germany.

Abstract

The dihydrido amine complex [Ru(H)(2)PMe(3){HN(CH(2)CH(2)P(i)Pr(2))(2)}] and H(2)O exhibit highly unusual, stereoselective H(+)/H(-) exchange, as derived using (1)H 2D EXSY NMR spectroscopy. While H(RuA) rapidly exchanges with H(2)O [k = 337(20) L mol(-1) s(-1)], no direct H(RuB)/H(2)O proton exchange was detected. Methylation of the pincer amine nitrogen results in unselective slow exchange of both hydrides with H(2)O. These results emphasize the important role of hydrogen bonding of N with Brønsted acids (e.g., water) for heteroloytic H(2) activation with Ru-amide hydrogenation catalysts, which was confirmed computationally.

PMID:
19950990
DOI:
10.1021/ja908644n
[Indexed for MEDLINE]
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