Interplay between Cationic and Neutral Species in the Rhodium-Catalyzed Hydroaminomethylation Reaction

Delphine Crozet, Aitor Gual, David McKay, Chiara Dinoi, Cyril Godard, Martine Urrutigoity, Jean-Claude Daran, Laurent Maron*, Carmen Claver, Philippe Kalck

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

33 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)7128-7140
Number of pages13
JournalChemistry - A European Journal
Volume18
Issue number23
DOIs
Publication statusPublished - Jun 2012

Keywords

  • coordination chemistry
  • density functional calculations
  • hydroaminomethylation
  • NMR spectroscopy
  • rhodium
  • HIGHLY SELECTIVE HYDROAMINOMETHYLATION
  • TANDEM REACTION SEQUENCES
  • HYDROGENATION REACTIONS
  • ASYMMETRIC HYDROFORMYLATION
  • 5-COORDINATE COMPLEXES
  • SYNTHETIC APPLICATIONS
  • DIHYDROGEN COMPLEXES
  • CHIRAL LIGANDS
  • LINEAR AMINES
  • BITE ANGLE

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