Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex

被引：13

作者：

Wilson, Henry H. ^{[1
]}

Yu, Xiaojuan ^{[2
]}

Cheisson, Thibault ^{[1
,3
]}

Smith, Patrick W. ^{[4
]}

Pandey, Pragati ^{[1
]}

Carroll, Patrick J. ^{[1
]}

Minasian, Stefan G. ^{[4
]}

Autschbach, Jochen ^{[2
]}

Schelter, Eric J. ^{[1
]}

机构：

[1] Univ Penn, Dept Chem, P Roy & Diana T Vagelos Labs, Philadelphia, PA 19104 USA

[2] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA

[3] Eramet Ideas, 1 Rue Albert Einstein, F-78190 Trappes, France

[4] Lawrence Berkeley Natl Lab, Berkeley, CA 94720 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2023年 / 145卷 / 02期

基金：

美国国家科学基金会;

关键词：

LANTHANIDE METAL ATOMS; REACTION-PRODUCTS; INFRARED-SPECTRA; BOND FORMATION; IMIDO; REACTIVITY; CHEMISTRY; SPECTROSCOPY; THORIUM(IV); METATHESIS;

D O I：

10.1021/jacs.2c12145

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Complexes featuring lanthanide-ligand multiple bonds are rare and highly reactive. They are important synthetic targets to understand 4f/5d-bonding in comparison to d-block and actinide congeners. Herein, the isolation and characterization of a bridging cerium(IV)-nitride complex: [(TriNOx)Ce(Li2 mu-N)Ce(TriNOx)][BArF4] is reported, the first example of a molecular cerium-nitride. The compound was isolated by deprotonating a monometallic cerium(IV)-ammonia complex: [CeIV(NH3)-(TriNOx)][BArF4]. The average Ce=N bond length of [(TriNOx)Ce(Li2 mu-N)Ce(TriNOx)][BArF4] was 2.117(3) angstrom. Vibrational studies of the 15N-isotopomer exhibited a shift of the Ce=N=Ce asymmetric stretch from v = 644 cm-1 to 640 cm-1, and X-ray spectroscopic studies confirm the +4 oxidation state of cerium. Computational analyses showed strong involvement of the cerium 4f shell in bonding with overall 16% and 11% cerium weight in the a- and N-bonds of the Ce=N=Ce fragment, respectively.

引用

页码：781 / 786

页数：6

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