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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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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Abstract 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.
AbstractList 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.
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.
Author Schmedt auf der Günne, Jörn
Drees, Markus
Schneider, Sven
Friedrich, Anja
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Snippet 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...
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...
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StartPage 17552
SubjectTerms Hydrogen Bonding
Magnetic Resonance Spectroscopy
Protons
Stereoisomerism
Substrate Specificity
Title Highly Stereoselective Proton/Hydride Exchange: Assistance of Hydrogen Bonding for the Heterolytic Splitting of H2
URI http://dx.doi.org/10.1021/ja908644n
https://www.ncbi.nlm.nih.gov/pubmed/19950990
https://search.proquest.com/docview/734165373
Volume 131
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