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Probing the catalytic potential of chloro nitrosyl rhenium(I) complexes


Jiang, Yanfeng; Blacque, Olivier; Berke, Heinz (2011). Probing the catalytic potential of chloro nitrosyl rhenium(I) complexes. Dalton Transactions, 40(11):2578-2587.

Abstract

The reduction of the mononitrosyl Re(II) salt NMe(4)](2)ReCl(5)(NO)] (1) with zinc in acetonitrile afforded the Re(I) dichloride complex ReCl(2)(NO)(CH(3)CN)(3)] (2). Subsequent ligand substitution reactions with PCy(3), PiPr(3) and P(p-tolyl) (3) afforded the bisphosphine Re(I) complexes ReCl(2)(NO)(PR(3))(2)(CH(3)CN)] (3, R = Cy a, iPr b, p-tolyl c) in good yields. The acetonitrile ligand in 3 is labile, permitting its replacement with H(2) (1 bar) to afford the dihydrogen Re(I) complexes ReCl(2)(NO)(PR(3))(2)(eta(2)-H(2))] (4, R = Cy a, iPr b). The catalytic activity of 2, 3 and 4 in hydrogen-related catalyses including dehydrocoupling of Me(2)NH center dot BH(3), dehydrogenative silylation of styrenes, and hydrosilylation of ketones and aryl aldehydes were investigated, with the main focus on phosphine and halide effects. In the dehydrocoupling of Me(2)NH center dot BH(3), the phosphine-free complex 2 exhibits the same activity as the bisphosphine-substituted systems. In the dehydrogenative silylation of styrenes, 3a and 4a bearing PCy(3) ligands exhibit high catalytic activities. Monochloro Re(I) hydrides Re(Cl)(H)(NO)(PR(3))(2)(CH(3)CN)] (5, R = Cy a, iPr b) were proven to be formed in the initiation pathway. The phosphine-free complex 2 showed in dehydrogenative silylations even higher activity than the bisphosphine derivatives, which further emphasizes the importance of a facile phosphine dissociation in the catalytic process. In the hydrosilylation of ketones and aryl aldehydes, at least one rhenium-bound phosphine is required to ensure high catalytic activity.

Abstract

The reduction of the mononitrosyl Re(II) salt NMe(4)](2)ReCl(5)(NO)] (1) with zinc in acetonitrile afforded the Re(I) dichloride complex ReCl(2)(NO)(CH(3)CN)(3)] (2). Subsequent ligand substitution reactions with PCy(3), PiPr(3) and P(p-tolyl) (3) afforded the bisphosphine Re(I) complexes ReCl(2)(NO)(PR(3))(2)(CH(3)CN)] (3, R = Cy a, iPr b, p-tolyl c) in good yields. The acetonitrile ligand in 3 is labile, permitting its replacement with H(2) (1 bar) to afford the dihydrogen Re(I) complexes ReCl(2)(NO)(PR(3))(2)(eta(2)-H(2))] (4, R = Cy a, iPr b). The catalytic activity of 2, 3 and 4 in hydrogen-related catalyses including dehydrocoupling of Me(2)NH center dot BH(3), dehydrogenative silylation of styrenes, and hydrosilylation of ketones and aryl aldehydes were investigated, with the main focus on phosphine and halide effects. In the dehydrocoupling of Me(2)NH center dot BH(3), the phosphine-free complex 2 exhibits the same activity as the bisphosphine-substituted systems. In the dehydrogenative silylation of styrenes, 3a and 4a bearing PCy(3) ligands exhibit high catalytic activities. Monochloro Re(I) hydrides Re(Cl)(H)(NO)(PR(3))(2)(CH(3)CN)] (5, R = Cy a, iPr b) were proven to be formed in the initiation pathway. The phosphine-free complex 2 showed in dehydrogenative silylations even higher activity than the bisphosphine derivatives, which further emphasizes the importance of a facile phosphine dissociation in the catalytic process. In the hydrosilylation of ketones and aryl aldehydes, at least one rhenium-bound phosphine is required to ensure high catalytic activity.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2011
Deposited On:14 Mar 2012 13:38
Last Modified:05 Apr 2016 15:41
Publisher:Royal Society of Chemistry
ISSN:1477-9226
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1039/c0dt00842g
Other Identification Number:ISI:000288030500023

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