Ammonia Synthesis by Hydrogenolysis of Titanium-Nitrogen Bonds Using Proton Coupled Electron Transfer

被引：66

作者：

Pappas, Iraklis ^{[1
]}

Chirik, Paul J. ^{[1
]}

机构：

[1] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 10期

关键词：

CATALYTIC-REDUCTION; BASICITY SCALE; ATOM TRANSFER; TI-III; DINITROGEN; COMPLEXES; CLEAVAGE; HYDROGENATION; METALLOCENES; REACTIVITY;

D O I：

10.1021/jacs.5b01047

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The catalytic hydrogenolysis of the titaniumamide bond in (eta(5)-C5Me4SiMe3)(2)Ti(Cl)NH2 to yield free ammonia is described. The rhodium hydride, (eta(5)-C5Me5)(py-Ph)RhH (py-Ph = 2-phenylpyridine), serves as the catalyst and promotes N-H bond formation via hydrogen atom transfer. The N-H bond dissociation free energies of ammonia ligands have also been determined for titanocene and zirconocene complexes and reveal a stark dependence on metal identity and oxidation state. In all cases, the N-H BDFEs of coordinated NH3 decreases by >40 kcal/mol from the value in the free gas phase molecule.

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页码：3498 / 3501

页数：4

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