Peer-Reviewed Journal Details
Mandatory Fields
Sung S.;Boon J.;Lee J.;Rajabi N.;Macgregor S.;Krämer T.;Young R.
2017
April
Organometallics
Convergent (De)Hydrogenative Pathways via a Rhodium α-Hydroxylalkyl Complex
Published
()
Optional Fields
36
8
1609
1617
© 2017 American Chemical Society. 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.
0276-7333
10.1021/acs.organomet.7b00158
Grant Details