溶剂化和无碱铈（III）混合夹层配合物的合成与表征

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-02-12 DOI:10.1021/acs.inorgchem.4c04840

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

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引用次数: 0

摘要

一系列溶剂化配合物[(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 - =二苯并环二烯醚；描述了由可变环戊二烯（Cp -）和环戊四烯（COT2 -）配体组成的早期镧系金属铈和镧的Ln = Ce, La)、[(dbCOT)Ce(C5Me5)(DME)] （Ce-7）和[(hdcCOT)Ce(C5Me5)(DME)] （Ce-8）和[(C8H8)Ce(C5Me5)] （Ce-9）、[(C8H8)Ce(C5Me4H) （Ce-10）和[(hdcCOT)Ce(C5Me5)] （Ce-11）混合夹心配合物。为了评价环戊二烯和环四烯配体对这些配合物特性的影响，研究了它们的固态结构、电化学和光物理性质，并进行了理论计算。为了进一步评价配体对配合物拓扑结构和还原性的影响，研究人员合成了几种无碱同系物，首次分离出了无碱单体和聚合物Ce（III）混合夹层化合物。

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

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

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. 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.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.