Silica Supported Organometallic IrI Complexes Enable Efficient Catalytic Methane Borylation

Staples, Orion; Ferrandon, Magali S.; Laurent, Guillaume P.; Kanbur, Uddhav; Kropf, A. Jeremy; Gau, Michael R.; Carroll, Patrick J.; McCullough, Katherine; Sorsche, Dieter; Perras, Frédéric A.; Delferro, Massimiliano; Kaphan, David M.; Mindiola, Daniel J.

doi:10.1021/jacs.2c13612

Silica Supported Organometallic Ir^I Complexes Enable Efficient Catalytic Methane Borylation

Journal Article · Thu Mar 30 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c13612· OSTI ID:2283740

Staples, Orion ^[1]; Ferrandon, Magali S. ^[2]; Laurent, Guillaume P. ^[3]; Kanbur, Uddhav ^[2]; Kropf, A. Jeremy ^[2]; ^[1]; Carroll, Patrick J. ^[1]; McCullough, Katherine ^[2]; ^[1]; ^[4]; ^[2]; ^[2]; ^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Ames Laboratory (AMES), Ames, IA (United States); Centre National de la Recherche Scientifique (CNRS) (France); Sorbonne Univ., Paris (France)
Ames Lab., and Iowa State Univ., Ames, IA (United States)

Catalytic C–H borylation is an attractive method for the conversion of the most abundant hydrocarbon, methane (CH₄), to a mild nucleophilic building block. However, existing CH₄ borylation catalysts often suffer from low turnover numbers and conversions, which is hypothesized to result from inactive metal hydride agglomerates. Herein we report that the heterogenization of a bisphosphine molecular precatalyst, [(dmpe)Ir(cod)CH₃], onto amorphous silica dramatically enhances its performance, yielding a catalyst that is 12-times more efficient than the current standard for CH₄ borylation. The catalyst affords over 2000 turnovers at 150 °C in 16 h with a selectivity of 91.5% for mono- vs diborylation. Higher catalyst loadings improve yield and selectivity for the monoborylated product (H₃CBpin) with 82.8% yield and >99% selectivity being achieved with 1255 turnovers. X-ray absorption and dynamic nuclear polarization-enhanced solid-state NMR spectroscopic studies identify the supported precatalyst as an Ir^I species, and indicate that upon completion of catalysis, multinuclear Ir polyhydrides are not formed. This is consistent with the hypothesis that immobilization of the organometallic Ir species on a surface prevents bimolecular decomposition pathways. Importantly, immobilization of the homogeneous Ir^I fragment onto amorphous silica represents a unique and simple strategy to improve the TON and longevity of a CH₄ borylation catalyst.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Ames Laboratory (AMES), Ames, IA (United States)

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

Grant/Contract Number:: SC0023340; AC02-06CH11357; AC02-07CH11358

OSTI ID:: 2283740

Alternate ID(s):: OSTI ID: 2573750

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 14 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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