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Permanent URL to this publication: http://dx.doi.org/10.5167/uzh-21033

Jiang, Y; Blacque, O; Frech, C M; Fox, T; Berke, H (2009). Development of Rhenium Catalysts for Amine Borane Dehydrocoupling and Transfer Hydrogenation of Olefins. Organometallics, 28(18):5493-5504.

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Five-coordinated rhenium(I) hydride complexes of the type [Re(Br)(H)(NO)(PR3)2] (R = Cy 2a, iPr 2b) were prepared from [Re(Br)2(NO)(PR3)2(η2-H2)] (R = Cy 1a, iPr 1b) via deprotonation of the η2-H2 ligands with various bases. Filling the vacant site of 2a or 2b by various less bulky two-electron donors produced the 18-electron complexes [Re(Br)(H)(NO)(PR3)2(L)] (L = O2 3, CH2═CH2 4, acetylene 5, H2 6, CO 7, CH3CN 8). The influence of the trans-coordinated ligand on the Re−H bond was examined. The 1H NMR chemical shift of the hydride depends on L in the order O2 > acetylene > CH2═CH2 > H2 > CO > CH3CN. The reactions of 2a or 2b with the IMes or SIMes ligands afforded the five-coordinated complex [Re(Br)(H)(NO)(PR3)(NHC)] (NHC = IMes 9 (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), SIMes 10 (SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene)) via replacement of one phosphine. The reaction of 2a or 2b with n-BuLi leads to the formation of the n-butene-coordinated dihydride complexes [Re(H)2(NO)(PR3)2(η2-n-CH2═CHC2H5)] (R = Cy 12a, iPr 12b). Species 1a and 1b reacted also with NaNMe2·BH3, affording the tetrahydride complexes [Re(H)4(NO)(PR3)2] (R = Cy 14a, iPr 14b) via the intermediacy of 2a and 2b. The molecular structures of complexes 8b, 10a, and 10b were established by single-crystal X-ray diffraction studies. The five-coordinated rhenium(I) hydride complexes 2a, 2b, 9a, and 9b catalyzed the dehydrocoupling of Me2NH·BH3 and the transfer hydrogenation of olefins using Me2NH·BH3 as a hydrogen donor, which showed high activities. Mechanistic studies were carried out indicating that these rhenium(I) hydride catalyses allowed formation of dihydrogen hydride complexes. A plausible catalytic cycle for both dehydrocoupling and transfer hydrogenation was proposed, which implies the ability of rhenium(I) complexes to activate B−H and N−H bonds by the facile redox interplay of Re(I) and Re(III) species.


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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Date:September 2009
Deposited On:14 Oct 2009 08:44
Last Modified:05 Apr 2016 13:22
Publisher:American Chemical Society
Publisher DOI:10.1021/om900458e
Official URL:http://pubs.acs.org

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