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Communication

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

Supporting Info

Anja Friedrich^†, Markus Drees^†, J

rn Schmedt auf der G

nne*^‡ and Sven Schneider*^†

Department Chemie, Technische Universit

t M

nchen, Lichtenbergstrasse 4, 85747 Garching b. M

nchen, Germany, and Department Chemie und Biochemie, Ludwig-Maximilians-Universit

t M

nchen, Butenandtstrasse 5-13, 81377 M

nchen, Germany

J. Am. Chem. Soc., 2009, 131 (48), pp 17552–17553

DOI: 10.1021/ja908644n

Publication Date (Web): November 12, 2009

gunch@cup.uni-muenchen.de; sven.schneider@ch.tum.de, †

Technische Universitt Mnchen.

, ‡

Ludwig-Maximilians-Universitt Mnchen.

Abstract

The dihydrido amine complex [Ru(H)₂PMe₃{HN(CH₂CH₂PⁱPr₂)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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History

Published In Issue December 09, 2009
Article ASAPNovember 12, 2009
Received: October 11, 2009

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Communication

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