Activation of Dinitrogen Promoted by Adsorption of C6H6 on Fe2VC- Cluster Anions

被引：2

作者：

Cheng, Xin ^{[1
,2
,3
]}

Li, Zi-Yu ^{[1
,3
]}

Jiang, Gui-Duo ^{[1
,2
,3
]}

Liu, Xiao-Xiao ^{[1
,2
,3
]}

Liu, Qing-Yu ^{[1
,3
]}

He, Sheng-Gui ^{[1
,2
,3
]}

机构：

[1] Chinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Specie, Beijing 100190, Peoples R China

[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China

[3] CAS Res Educ Ctr Excellence Mol Sci, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2023年 / 14卷 / 28期

基金：

中国国家自然科学基金;

关键词：

CARBON-DIOXIDE ACTIVATION; ROOM-TEMPERATURE; N-2; BENZENE; COMPLEXES; CHEMISTRY; MECHANISM; CLEAVAGE; BINDING; BONDS;

D O I：

10.1021/acs.jpclett.3c01367

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The introduction of organic ligands is one of the effectivestrategiesto improve the stability and reactivity of metal clusters. Herein,the enhanced reactivity of benzene-ligated cluster anions Fe2VC(C6H6)(-) with respect to naked Fe2VC- is identified. Structuralcharacterization suggests that C6H6 is molecularlybound to the dual metal site in Fe2VC(C6H6)(-). Mechanistic details reveal that thecleavage of N N is feasible in Fe2VC(C6H6)(-)/N-2 but hindered by anoverall positive barrier in the Fe2VC-/N-2 system. Further analysis discloses that the ligatedC(6)H(6) regulates the compositions and energy levelsof the active orbitals of the metal clusters. More importantly, C6H6 serves as an electron reservoir for the reductionof N-2 to lower the crucial energy barrier of N Nsplitting. This work demonstrates that the flexibility of C6H6 in terms of withdrawing and donating electrons is crucialto regulating the electronic structures of the metal cluster and enhancingthe reactivity.

引用

页码：6431 / 6436

页数：6

共 54 条

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