Interplay between Cationic and Neutral Species in the Rhodium‐Catalyzed Hydroaminomethylation Reaction |
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| Authors: | Dr Delphine Crozet Dr Aitor Gual Dr David McKay Dr Chiara Dinoi Dr Cyril Godard Prof Martine Urrutigoïty Dr Jean‐Claude Daran Prof Laurent Maron Prof Carmen Claver Prof Philippe Kalck |
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| Institution: | 1. Laboratoire de Chimie de Coordination UPR CNRS 8241, Composante ENSIACET, Université de Toulouse UPS‐INP‐LCC, 4 allée Emile Monso BP 44362, 31030 Toulouse Cedex 4 (France);2. Departament de Quimica Fisica i Inorganica, Universitat Rovira i Virgili, C/Marcel?li Domingo s/n, 43007 Tarragona (Spain);3. LPCNO, UMR 5215, Université de Toulouse‐CNRS, INSA, UPS, 135 avenue de Rangueil, 31077 Toulouse Cedex 4 (France);4. Laboratoire de Chimie de Coordination, CNRS UPR 8241, Université de Toulouse UPS‐INP‐LCC, 205, Route de Narbonne, 31077 Cedex 04 (France) |
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| Abstract: | The reactivity of Rh(CO)2{(R,R)‐Ph? BPE}]BF4 ( 2 ) toward amine, CO and/or H2 was examined by high‐pressure NMR and IR spectroscopy. The two cationic pentacoordinated species Rh(CO)3{(R,R)‐Ph? BPE}]BF4 ( 4 ) and Rh(CO)2(NHC5H10){(R,R)‐Ph‐BPE}]BF4 ( 8 ) were identified. The transformation of 2 into the neutral complex RhH(CO)2{(R,R)‐Ph? BPE}] ( 3 ) under hydroaminomethylation conditions (CO/H2, amine) was investigated. The full mechanisms related to the formation of 3 , 4 and 8 starting from 2 are supported by DFT calculations. In particular, the pathway from 2 to 3 revealed the deprotonation by the amine of the dihydride species Rh(H)2(CO)2{(R,R)‐Ph? BPE}]BF4 ( 6 ), resulting from the oxidative addition of H2 on 2 . |
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| Keywords: | coordination chemistry density functional calculations hydroaminomethylation NMR spectroscopy rhodium |
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