UZH-Logo

Rhenium in Homogeneous Catalysis: ReBrH(NO)(labile ligand) (large-bite-angle diphosphine)] Complexes as Highly Active Catalysts in Olefin Hydrogenations


Dudle, B; Rajesh, K; Blacque, O; Berke, H (2011). Rhenium in Homogeneous Catalysis: ReBrH(NO)(labile ligand) (large-bite-angle diphosphine)] Complexes as Highly Active Catalysts in Olefin Hydrogenations. Journal of the American Chemical Society, 133(21):8168-8178.

Abstract

The reaction of ReBr(2)(MeCN)(NO)(P boolean AND P)] (P boolean AND P = 1,1'-bisdiphenylphosphinoferrocene (dppfc) (la), 1,1'-bisriiisopropylphosphinopherrocene (diprpfc) (1b), 2,2'-bis(diphenylphosphino)diphenyi ether (dpephos) (1c), 10,11-dihydro-4,5bis(diphenylphosphino)dibenzobf]oxepine (homoxantphos) (1d) and 4,6-bis(diphenylphosphino)-10,10-dimethylphenoxasilin (Sixantphos) (1e)) led in the presence of HSiEt(3) and ethylene to formation of the ethylene hydride complexes ReBrH(eta(2)-C(2)H(4))(NO)(P boolean AND P)] (3a,b,d), the MeCN ethyl complex ReBr(Et)(MeCN)(NO)(dpephos)] (5c) and two ortho-metalated stereoisomers ReBr(eta(2)-C(2)H(4))(NO)(eta(3)-o-C(6)H(4)-Sixantphos)] 8e(up) and 8e(down). The complexes 3a,b,d, and 5c and the isomers of 8e showed high catalytic activity (TOFs ranging from 22 to 4870 h(-1), TONs up to 24000) in the hydrogenation of monosubstituted olefins. For 8e(down) and 8e(up) a remarkable functional group tolerance and catalyst stability were noticed. Kinetic experiments revealed k(obs) to be first order in c(cat) and c(H(2)) and zeroth order in c(olefin). Mechanistic studies and DFT calculations suggest the catalysis to proceed along an Osborn-type catalytic cycle with olefin before H2 addition. The unsaturated key intermediates ReBrH(NO)(P boolean AND P)] (2a-e) could be intercepted with MeCN as ReBrH(MeCN)(NO)(P boolean AND P)] (10a-d) complexes or isolated as dimeric mu(2)-(H)(2) complexes {ReBr(mu(2)-H)(NO)(P boolean AND P)}(2)] (9b and 9e). Variation of the bidentate ligand demonstrated a crucial influence of the (large)-bite-angle on the catalytic performance and reactivity of 3a,b,d, 5c, and 8e.

The reaction of ReBr(2)(MeCN)(NO)(P boolean AND P)] (P boolean AND P = 1,1'-bisdiphenylphosphinoferrocene (dppfc) (la), 1,1'-bisriiisopropylphosphinopherrocene (diprpfc) (1b), 2,2'-bis(diphenylphosphino)diphenyi ether (dpephos) (1c), 10,11-dihydro-4,5bis(diphenylphosphino)dibenzobf]oxepine (homoxantphos) (1d) and 4,6-bis(diphenylphosphino)-10,10-dimethylphenoxasilin (Sixantphos) (1e)) led in the presence of HSiEt(3) and ethylene to formation of the ethylene hydride complexes ReBrH(eta(2)-C(2)H(4))(NO)(P boolean AND P)] (3a,b,d), the MeCN ethyl complex ReBr(Et)(MeCN)(NO)(dpephos)] (5c) and two ortho-metalated stereoisomers ReBr(eta(2)-C(2)H(4))(NO)(eta(3)-o-C(6)H(4)-Sixantphos)] 8e(up) and 8e(down). The complexes 3a,b,d, and 5c and the isomers of 8e showed high catalytic activity (TOFs ranging from 22 to 4870 h(-1), TONs up to 24000) in the hydrogenation of monosubstituted olefins. For 8e(down) and 8e(up) a remarkable functional group tolerance and catalyst stability were noticed. Kinetic experiments revealed k(obs) to be first order in c(cat) and c(H(2)) and zeroth order in c(olefin). Mechanistic studies and DFT calculations suggest the catalysis to proceed along an Osborn-type catalytic cycle with olefin before H2 addition. The unsaturated key intermediates ReBrH(NO)(P boolean AND P)] (2a-e) could be intercepted with MeCN as ReBrH(MeCN)(NO)(P boolean AND P)] (10a-d) complexes or isolated as dimeric mu(2)-(H)(2) complexes {ReBr(mu(2)-H)(NO)(P boolean AND P)}(2)] (9b and 9e). Variation of the bidentate ligand demonstrated a crucial influence of the (large)-bite-angle on the catalytic performance and reactivity of 3a,b,d, 5c, and 8e.

Citations

33 citations in Web of Science®
35 citations in Scopus®
Google Scholar™

Altmetrics

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:June 2011
Deposited On:12 Mar 2012 14:29
Last Modified:05 Apr 2016 15:41
Publisher:American Chemical Society
ISSN:0002-7863
Publisher DOI:10.1021/ja107245k
Other Identification Number:ISI:000291459100029

Download

Full text not available from this repository.View at publisher

TrendTerms

TrendTerms displays relevant terms of the abstract of this publication and related documents on a map. The terms and their relations were extracted from ZORA using word statistics. Their timelines are taken from ZORA as well. The bubble size of a term is proportional to the number of documents where the term occurs. Red, orange, yellow and green colors are used for terms that occur in the current document; red indicates high interlinkedness of a term with other terms, orange, yellow and green decreasing interlinkedness. Blue is used for terms that have a relation with the terms in this document, but occur in other documents.
You can navigate and zoom the map. Mouse-hovering a term displays its timeline, clicking it yields the associated documents.

Author Collaborations