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

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

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

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
JournalOrganometallics
Volume36
Issue number8
Early online date14 Apr 2017
DOIs
Publication statusPublished - 24 Apr 2017

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Sung, S., Boon, J. K., Lee, J. J. C., Rajabi, N. A., Macgregor, S. A., Krämer, T., & Young, R. D. (2017). Convergent (De)Hydrogenative Pathways via a Rhodium α-Hydroxylalkyl Complex. Organometallics, 36(8), 1609-1617. https://doi.org/10.1021/acs.organomet.7b00158

Convergent (De)Hydrogenative Pathways via a Rhodium α-Hydroxylalkyl Complex. / Sung, Simon; Boon, Jie Kang; Lee, Johnathan J.C.; Rajabi, Nasir A.; Macgregor, Stuart A.; Krämer, Tobias; Young, Rowan D.

In: Organometallics, Vol. 36, No. 8, 24.04.2017, p. 1609-1617.

Research output: Contribution to journalArticle

Sung, S, Boon, JK, Lee, JJC, Rajabi, NA, Macgregor, SA, Krämer, T & Young, RD 2017, 'Convergent (De)Hydrogenative Pathways via a Rhodium α-Hydroxylalkyl Complex', Organometallics, vol. 36, no. 8, pp. 1609-1617. https://doi.org/10.1021/acs.organomet.7b00158
Sung, Simon ; Boon, Jie Kang ; Lee, Johnathan J.C. ; Rajabi, Nasir A. ; Macgregor, Stuart A. ; Krämer, Tobias ; Young, Rowan D. / Convergent (De)Hydrogenative Pathways via a Rhodium α-Hydroxylalkyl Complex. In: Organometallics. 2017 ; Vol. 36, No. 8. pp. 1609-1617.
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AB - 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.

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