Low-Valent Iron Mono-Diazadiene Compounds: Electronic Structure and Catalytic Application

被引：44

作者：

Lichtenberg, Crispin ^{[1
]}

Adelhardt, Mario ^{[2
]}

Gianetti, Thomas L. ^{[1
]}

Meyer, Karsten ^{[2
]}

de Bruin, Bas ^{[3
]}

Gruetzmacher, Hansjoerg ^{[1
]}

机构：

[1] ETH, Dept Chem & Appl Biosci, CH-8093 Zurich, Switzerland

[2] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany

[3] Univ Amsterdam, Fac Sci, Dept Homogeneous Catalysis, vant Hoff Inst Mol Sci, NL-1090 GS Amsterdam, Netherlands

来源：

ACS CATALYSIS | 2015年 / 5卷 / 10期

基金：

瑞士国家科学基金会;

关键词：

iron diazadiene compounds; electronic structure determination; methylamine-borane; dehydrogenative polymerization; homogeneous catalysis; AMINE-BORANE ADDUCTS; AMMONIA-BORANE; SPIN-STATE; ALPHA-DIIMINE; BASIS-SETS; COMPLEXES; DEHYDROGENATION; LIGANDS; INNOCENT; ROUTE;

D O I：

10.1021/acscatal.5b01416

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：

A series of monodiazadiene diolefin iron compounds, [Fe(trop(2)dad)(L)] (4; L = neutral ligand), has been prepared by one-electron oxidation of the Fe-I species [NaFe-(trop(2)dad)(thf)(3)] (dad = diazadiene; trop = 5H-dibenzo[a,d]-cyclohepten-5-yl). The electronic structures of compounds 4 were investigated by NMR and Mossbauer spectroscopy, single-crystal X-ray diffraction, solid- and liquid-phase magnetic susceptibility measurements, and DFT calculations. Compounds of type 4 with labile ligands L were found to be active (pre)catalysts for the dehydrogenative coupling of (alkyl)amine-boranes. Remarkably high activities were observed, especially for the homogeneous dehydrogenative polymerization of methylamine-borane.

引用

页码：6230 / 6240

页数：11

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