Convergent (De)Hydrogenative Pathways via a Rhodium α-Hydroxylalkyl Complex

Simon Sung, Jie Kang Boon, Johnathan J. C. Lee, Nasir Ahmad Rajabi, Stuart Alan Macgregor, Tobias Krämer*, Rowan D. Young

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)
45 Downloads (Pure)


We report the convergent reaction pathways between [RhH(PPh3)4] and POP ketone (1) and alcohol (2) ligands that terminate in the formation of an α-hydroxylalkyl rhodium(I) complex (3), representing two halves of a formal reduction/oxidation pathway between 1 and 2. In the case of hydride transfer to 1, the formation of the α-hydroxylalkyl rhodium(I) complex (3) proceeds via a rare hydrido(2-carbonyl) complex (4). C-H activation in 2 at the proligand's central methine position, rather than O-H activation of the hydroxy motif, followed by loss of dihydrogen also generates the α-hydroxylalkyl rhodium(I) complex (3). The validity of the postulated reaction pathways is probed with DFT calculations. The observed reactivity supports α-hydroxylalkyl complexes as competent intermediates in ketone hydrogenation catalyzed by rhodium hydrides and suggest that ligands 1 and 2 may be "noninnocent" coligands in reported hydrogenation catalyst systems in which they are utilized.

Original languageEnglish
Pages (from-to)1609-1617
Number of pages9
Issue number8
Early online date14 Apr 2017
Publication statusPublished - 24 Apr 2017

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


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