Dinitrogen Insertion and Cleavage by a Metal-Metal Bonded Tricobalt(I) Cluster

被引：13

作者：

Eaton, Mary C. ^{[1
,2
]}

Catalano, Vincent J. ^{[3
]}

Shearer, Jason ^{[4
]}

Murray, Leslie J. ^{[1
,2
]}

机构：

[1] Univ Florida, Ctr Catalysis, Gainesville, FL 32611 USA

[2] Univ Florida, Florida Ctr Heterocycl Cpds, Dept Chem, Gainesville, FL 32611 USA

[3] Univ Nevada, Dept Chem, Reno, NV 89557 USA

[4] Trinity Univ, Dept Chem, San Antonio, TX 78212 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2021年 / 143卷 / 15期

基金：

美国国家卫生研究院; 美国国家科学基金会;

关键词：

CATALYTIC SILYLATION; AMMONIA-SYNTHESIS; COMPLEXES; STATE; IRON; ADSORPTION; REDUCTION; NITROGEN; LIGANDS;

D O I：

10.1021/jacs.1c01840

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reduction of a tricobalt(II) tri(bromide) cluster supported by a tris(beta-diketiminate) cyclophane results in halide loss, ligand compression, and metal-metal bond formation to yield a 48-electron Co-3(I) cluster, Co3LEt/Me (2). Upon reaction of 2 with dinitrogen, all metal-metal bonds are broken, steric conflicts are relaxed, and dinitrogen is incorporated within the internal cavity to yield a formally (mu(3)-eta(1):eta(2):eta(1)-dinitrogen)tricobalt(I) complex, 3. Broken symmetry DFT calculations (PBE0/def2-tzvp/D3) support an N-N bond order of 2.1 in the bound N-2 with the calculated N-N stretching frequency (1743 cm(-1)) comparable to the experimental value (1752 cm(-1)). Reduction of 3 under Ar in the presence of Me3SiBr results in N-2 scission with tris(trimethylsilyl)amine afforded in good yield.

引用

页码：5649 / 5653

页数：5

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