Reactivity of Iridium Complexes of a Triphosphorus-Pincer Ligand Based on a Secondary Phosphine. Catalytic Alkane Dehydrogenation and the Origin of Extremely High Activity

Gordon, Benjamin M.; Lease, Nicholas; Emge, Thomas J.; Hasanayn, Faraj; Goldman, Alan S.

doi:10.1021/jacs.1c13309

Reactivity of Iridium Complexes of a Triphosphorus-Pincer Ligand Based on a Secondary Phosphine. Catalytic Alkane Dehydrogenation and the Origin of Extremely High Activity

Journal Article · Sat Feb 26 23:00:00 EST 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c13309· OSTI ID:1866620

^[1]; Lease, Nicholas ^[2]; Emge, Thomas J. ^[2]; ^[3]; ^[2]

Rutgers, The State Univ. of New Jersey, Piscataway, NJ (United States); Rutgers University
Rutgers, The State Univ. of New Jersey, Piscataway, NJ (United States)
American Univ. of Beirut (Lebanon)

The selective functionalization of alkanes and alkyl groups is a major goal of chemical catalysis. Toward this end, a bulky triphosphine with a central secondary phosphino group, bis(2-di-t-butyl-phosphinophenyl)phosphine (^tBuP^HPP), has been synthesized. When complexed to iridium, it adopts a meridional (“pincer”) configuration. The secondary phosphino H atom can undergo migration to iridium to give an anionic phosphido-based–pincer (^tBuPPP) complex. Stoichiometric reactions of the (^tBuPPP)Ir complexes reflect a distribution of steric bulk around the iridium center in which the coordination site trans to the phosphido group is quite crowded; one coordination site cis to the phosphido is even more crowded; and the remaining site is particularly open. The (^tBuPPP)Ir precursors are the most active catalysts reported to date for dehydrogenation of n-alkanes, by about 2 orders of magnitude. The electronic properties of the iridium center are similar to that of well-known analogous (^RPCP)Ir catalysts. Accordingly, DFT calculations predict that (^tBuPPP)Ir and (^tBuPCP)Ir are, intrinsically, comparably active for alkane dehydrogenation. While dehydrogenation by (^RPCP)Ir proceeds through an intermediate trans-(PCP)IrH₂(alkene), (^tBuPPP)Ir follows a pathway proceeding via cis-(PPP)IrH₂(alkene), thereby circumventing unfavorable placement of the alkene at the bulky site trans to phosphorus. (^tBuPPP)Ir and (^tBuPCP)Ir, however, have analogous resting states: square planar (pincer)Ir(alkene). Alkene coordination at the crowded trans site is therefore unavoidable in the resting states. Furthermore, the resting state of the (^tBuPPP)Ir catalyst is destabilized by the architecture of the ligand, and this is largely responsible for its unusually high catalytic activity.

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Research Organization:: Rutgers Univ., Piscataway, NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0020139

OSTI ID:: 1866620

Alternate ID(s):: OSTI ID: 2001036

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 9 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
alkanes
alkyls
catalysis
dehydrogenation
free energy
hydrocarbons
ligands
olefins
organic reactions

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