Highly Stereoselective Proton/Hydride Exchange: Assistance of Hydrogen Bonding for the Heterolytic Splitting of H2

The dihydrido amine complex [Ru(H)2PMe3{HN(CH2CH2P i Pr2)2}] and H2O exhibit highly unusual, stereoselective H+/H− exchange, as derived using 1H 2D EXSY NMR spectroscopy. While H RuA rapidly exchanges with H2O [k = 337(20) L mol−1 s−1], no direct H RuB /H2O proton exchange was detected. Methylation...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 131; no. 48; pp. 17552 - 17553
Main Authors Friedrich, Anja, Drees, Markus, Schmedt auf der Günne, Jörn, Schneider, Sven
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 09.12.2009
Subjects
Hydrogen Bonding
Magnetic Resonance Spectroscopy
Protons
Stereoisomerism
Substrate Specificity
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Summary:The dihydrido amine complex [Ru(H)2PMe3{HN(CH2CH2P i Pr2)2}] and H2O exhibit highly unusual, stereoselective H+/H− exchange, as derived using 1H 2D EXSY NMR spectroscopy. While H RuA rapidly exchanges with H2O [k = 337(20) L mol−1 s−1], no direct H RuB /H2O proton exchange was detected. Methylation of the pincer amine nitrogen results in unselective slow exchange of both hydrides with H2O. These results emphasize the important role of hydrogen bonding of N with Brønsted acids (e.g., water) for heteroloytic H2 activation with Ru−amide hydrogenation catalysts, which was confirmed computationally.
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ISSN:0002-7863
1520-5126
DOI:10.1021/ja908644n