Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides

被引：26

作者：

Kiernicki, John J. ^{[1
]}

Shanahan, James R. ^{[1
]}

Zeller, Matthias ^{[2
]}

Szymczak, Nathaniel K. ^{[1
]}

机构：

[1] Univ Michigan, 930 N Univ, Ann Arbor, MI 48109 USA

[2] Purdue Univ, HC Brown Lab, 560 Oval Dr, W Lafayette, IN 47907 USA

来源：

CHEMICAL SCIENCE | 2019年 / 10卷 / 21期

关键词：

HYDROGEN EVOLUTION; BOND-CLEAVAGE; COMPLEXES; REACTIVITY; FE; OXIDATION; ELECTROCHEMISTRY; COORDINATION; NITROGENASE; REDUCTION;

D O I：

10.1039/c9sc00561g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Geometrically flexible 9-borabicyclo[3.3.1]nonyl units within the secondary coordination sphere enable isolation of high-spin Fe(ii)-dihydrides stabilized by boron-hydride interactions and a rare example of an isolable S = 3/2 reduction product. The borane-capped Fe(ii)-dihydride: (1) rapidly deprotonates E-H (E = N, O, P, S) bonds to afford borane-stabilized Fe adducts and (2) releases H-2 upon exposure to pi-acids. The Lewis acids provide an avenue for redox-leveling in analogy to the near constant operating potential for N-2 reduction in nitrogenase.

引用

页码：5539 / 5545

页数：7

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