Synthesis and Characterization of Solvated and Base-Free Cerium(III) Mixed-Sandwich Complexes

Pandey, Pragati; Zaichenko, Aleksandr; Smith, Patrick W.; Russo, Dominic R.; Gau, Michael R.; Carroll, Patrick J.; Keller, Taylor M.; Bacon, Alexandra M.; Minasian, Stefan G.; Autschbach, Jochen; Schelter, Eric J.

doi:10.1021/acs.inorgchem.4c04840

Synthesis and Characterization of Solvated and Base-Free Cerium(III) Mixed-Sandwich Complexes

Journal Article · Wed Feb 12 00:00:00 EST 2025 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.4c04840· OSTI ID:2587159

^[1]; Zaichenko, Aleksandr ^[2]; ^[3]; ^[3]; ^[1]; Carroll, Patrick J. ^[1]; Keller, Taylor M. ^[1]; Bacon, Alexandra M. ^[1]; ^[3]; ^[2]; ^[1]

University of Pennsylvania, University Park, PA (United States)
University at Buffalo, State University of New York, NY (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

A series of solvated complexes: [(C₈H₈)Ln(C₅Me₄R)(DME)] Ln = La, R = -Me; (La-2) Ln = Ce, R = -Me, -SiMe₃, -H; (Ce-2, Ce-3, Ce-4), [(dbCOT)Ln(C₅Me₅)(DME)] (Ln-6), (dbCOT^2- = dibenzocyclooctadienide; Ln = Ce, La), [(dbCOT)Ce(C₅Me₄H)(DME)] (Ce-7) and [(hdcCOT)Ce(C₅Me₅)(DME)] (Ce-8) (hdcCOT^2- = hexahydrodicyclopentacyclooctatetraenide) and base-free mixed-sandwich complexes [(C₈H₈)Ce(C₅Me₅)] (Ce-9), [(C₈H₈)Ce(C₅Me₄H) (Ce-10) and [(hdcCOT)Ce(C₅Me₅)] (Ce-11) of the early lanthanide metals cerium and lanthanum comprising variable cyclopentadienide (Cp^-) and cyclooctatetraenide (COT^2-) ligands is described. Here, to evaluate the effect of cyclopentadienide and cyclooctatetraenide ligands on the characteristics of these complexes, their solid-state structural, electrochemical, and photophysical properties were studied and accompanied by theoretical calculations. To further evaluate the effect of ligands on the topology of the complexes and the reducing properties of the complexes, syntheses of several base-free congeners were pursued, which led to isolation of the first base-free monomeric and polymeric Ce(III) mixed-sandwich compounds.

View Accepted Manuscript (DOE)

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; SC0020169

OSTI ID:: 2587159

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 7 Vol. 64; ISSN 0020-1669; ISSN 1520-510X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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