Rhenium in homogeneous catalysis: [ReBrH(NO)(labile ligand)(large-bite-angle diphosphine)] complexes as highly active catalysts in olefin hydrogenations |
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Authors: | Dudle Balz Rajesh Kunjanpillai Blacque Olivier Berke Heinz |
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Institution: | Institute of Inorganic Chemistry, University of Zu?rich, Winterthurerstrasse 190, CH-8057 Zu?rich. |
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Abstract: | The reaction of ReBr(2)(MeCN)(NO)(P∩P)] (P∩P = 1,1'-bisdiphenylphosphinoferrocene (dppfc) (1a), 1,1'-bisdiisopropylphosphinopherrocene (diprpfc) (1b), 2,2'-bis(diphenylphosphino)diphenyl ether (dpephos) (1c), 10,11-dihydro-4,5-bis(diphenylphosphino)dibenzob,f]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(η(2)-C(2)H(4))(NO)(P∩P)] (3a,b,d), the MeCN ethyl complex ReBr(Et)(MeCN)(NO)(dpephos)] (5c) and two ortho-metalated stereoisomers of ReBr(η(2)-C(2)H(4))(NO)(η(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 H(2) addition. The unsaturated key intermediates ReBrH(NO)(P∩P)] (2a-e) could be intercepted with MeCN as ReBrH(MeCN)(NO)(P∩P)] (10a-d) complexes or isolated as dimeric μ(2)-(H)(2) complexes {ReBr(μ(2)-H)(NO)(P∩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. |
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