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

Journal Article · · Inorganic Chemistry
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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), (dbCOT2- = dibenzocyclooctadienide; Ln = Ce, La), [(dbCOT)Ce(C5Me4H)(DME)] (Ce-7) and [(hdcCOT)Ce(C5Me5)(DME)] (Ce-8) (hdcCOT2- = 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 (COT2-) ligands is described. 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.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
US Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
2587159
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 7 Vol. 64
Country of Publication:
United States
Language:
English

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Related Subjects

Lanthanides
Ligands
Molecular structure
Molecules
Redox reactions