Electronic Structure Tuning of Lanthanidocene Photocatalysts for C–F Bond Cleavage

Tanuhadi, Elias; Katzer, Nicholas J.; Arnold, Polly L.

doi:10.1021/acs.inorgchem.5c04580

Title: Electronic Structure Tuning of Lanthanidocene Photocatalysts for C–F Bond Cleavage

Journal Article · Mon Dec 08 00:00:00 UTC 2025 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.5c04580 · OSTI ID:3030784

Tanuhadi, Elias ^[1];

^[1];

^[1]

University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

A set of nine new robust, tunable cerium complexes supported by an ansa-bis(cyclopentadienyl) ligand, [Me₂Si(η⁵-Cp^R)₂]CeX (^anCp^R)CeX, are excellent homogeneous visible-light photocatalysts for the monodefluoroalkylation of trifluorotoluene with Mg(CH₂C₆H₅)₂THF₂ (R = Me₄, SiMe₃, X = N(SiMe₃)₂ (N″), X = CH(SiMe₃)₂ (R''), Cl, OC₆H₂^tBu₂-2,6,Me-4 (OAr)). The trends in photocatalytic activity within the series are explained by photophysical spectroscopic analyses. The aryloxide complex [Me₂Si(Cp^SiMe3)₂]CeOAr, which has the highest activity (95% substrate conversion in 27 h), shows the most negative (most reducing) excited-state reduction potential (-2.71 V vs Fc). The precatalyst excited-state lifetimes are also exceptionally long. Detailed photoluminescence, NMR spectroscopic, and kinetic studies on chloride [Me₂Si(Cp^Me4)₂]CeCl suggest that the "ate" complex [{Me₂Si(Cp^Me4)₂}₂Ce^IIIClBn][MgBn] is the active catalyst in the alkylation reaction to form PhCF₂CH₂Ph with high selectivity over PhCF₂H. Finally, the reaction rates are up to 30 times higher than previously reported for organometallic rare-earth photocatalysts for these Ce complexes and comparable to established Ir-based photoredox systems.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 3030784

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 11 Vol. 65; ISSN 0020-1669; ISSN 1520-510X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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