Rhodium Complexes of 2,6-Bis(dialkylphosphinomethyl)pyridines: Improved C–H Activation, Expanded Reaction Scope, and Catalytic Direct Arylation

Gair, Joseph J.; Qiu, Yehao; Chan, Natalie H.; Filatov, Alexander S.; Lewis, Jared C.

doi:10.1021/acs.organomet.7b00532

Title: Rhodium Complexes of 2,6-Bis(dialkylphosphinomethyl)pyridines: Improved C–H Activation, Expanded Reaction Scope, and Catalytic Direct Arylation

Journal Article · Thu Nov 16 00:00:00 EST 2017 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.7b00532· OSTI ID:1437457

Gair, Joseph J. ^[1]; Qiu, Yehao ^[1]; Chan, Natalie H. ^[1]; Filatov, Alexander S. ^[1];

^[1]

Univ. of Chicago, IL (United States)

The reactivity of (PNP)Rh(Ph) (PNP = 2,6-bis(dialkylphosphinomethyl)pyridine) toward a variety of electrophiles (Ar–I, ArCH₂Cl, O₂, I₂, B₂pin₂, and ArSO₃H) was explored, and several new modes of oxidative reactivity were observed. We note substituting ^tBu₂P for ⁱPr₂P provided 100-fold rate enhancement toward C–H bond activation and addressed the previously reported challenge of N₂ inhibition. Studying the stoichiometric reactivity of (PNP)Rh complexes toward C–H cleavage and oxidative functionalization led to (PNP)Rh-catalyzed cross-coupling of aryl iodides with sp² and sp³ C–H bonds.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation ((NSF); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357; NSF/CHE-1346572; NSF/DMR-1531283

OSTI ID:: 1437457

Journal Information:: Organometallics, Vol. 36, Issue 24; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 16 works

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