One-Electron Reduction of Constrained and Unsymmetric Diiron Dinitrogen Complexes

被引：7

作者：

Feng, Rui ^{[1
]}

Jiang, Yang ^{[2
]}

Shi, Xianghui ^{[1
]}

Wang, Xueli ^{[1
]}

Chen, Wang ^{[2
,3
]}

Xie, Fei

Su, Jie ^{[4
]}

Wei, Junnian ^{[1
]}

Ye, Shengfa ^{[2
]}

Xi, Zhenfeng ^{[1
]}

机构：

[1] Peking Univ, Beijing Natl Lab Mol Sci BNLMS, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China

[2] Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China

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

[4] Peking Univ, Coll Chem, Beijing Natl Lab Mol Sci BNLMS, Beijing 100871, Peoples R China

来源：

CCS CHEMISTRY | 2023年 / 5卷 / 11期

基金：

北京市自然科学基金; 中国国家自然科学基金; 中国博士后科学基金;

关键词：

diiron dinitrogen complexes; dinitrogen fixation; constrained geometry; one-electron reduction; IRON; N-2; ACTIVATION; COORDINATION; CLEAVAGE; CHEMISTRY; SURFACES; BINDING; ATOMS;

D O I：

10.31635/ccschem.023.202303053

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Iron sites in both nitrogenase enzymes and chemical catalysts for N2 fixation are typically at constrained distances and angles. Herein, we report a one -electron reduction reaction realized by constrained diiron dinitrogen cores. Using the semicircular bis (& beta;-diketiminate) ligand, a series of diiron dinitrogen complexes were synthesized, in which the N2 groups were allowed to bind with Fe-CtN2-Fe angles ranging from 154 & DEG; to 158 & DEG; (CtN2 = centroid of N2). One -electron reduction of complex 2a [LFe(& mu;-N2)Fe(Et2O)] gave dimer product 3a [LFe(& mu;-N2)FeK]2(& mu;-N2) or monomer 3b [LFe(& mu;-N2)Fe(DMAP)K]. Based on superconducting quantum interference device measurements and density functional theory calculations, 2a, 3a, and 3b exhibited ground spin states of S = 3, S = 5, and S = 5/2, respectively. In addition, complex 3 underwent N2 derivatization via a silylation pathway followed by an acidic cleavage to yield N2H4 as the product.

引用

页码：2473 / 2481

页数：9

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