Five-Coordinate Low-Spin {FeNO}7 PNP Pincer Complexes

被引：11

作者：

Pecak, Jan ^{[1
]}

Stoeger, Berthold ^{[2
]}

Mastalir, Matthias ^{[1
]}

Veiros, Luis F. ^{[3
]}

Ferreira, Liliana P. ^{[4
,5
]}

Pignitter, Marc ^{[6
]}

Linert, Wolfgang ^{[1
]}

Kirchner, Karl ^{[1
]}

机构：

[1] Vienna Univ Technol, Inst Appl Synthet Chem, Getreidemarkt 9, A-1060 Vienna, Austria

[2] Vienna Univ Technol, Xray Ctr, Getreidemarkt 9, A-1060 Vienna, Austria

[3] Univ Lisbon, Inst Super Tecn, Ctr Quim Estrutural, Ave Rovisco Pais 1, P-1049001 Lisbon, Portugal

[4] Univ Lisbon, Fac Ciencias, Biosyst & Integrat Sci Inst, P-1749016 Lisbon, Portugal

[5] Univ Coimbra, Dept Phys, P-3004516 Coimbra, Portugal

[6] Univ Vienna, Dept Physiol Chem, Fac Chem, Althanstr 14, A-1090 Vienna, Austria

来源：

INORGANIC CHEMISTRY | 2019年 / 58卷 / 07期

基金：

奥地利科学基金会;

关键词：

GAUSSIAN-BASIS SETS; MOLECULAR CALCULATIONS; ELECTRONIC-STRUCTURE; DFT CALCULATIONS; IRON; AMINES; PSEUDOPOTENTIALS; ALCOHOLS; BEARING; APPROXIMATION;

D O I：

10.1021/acs.inorgchem.9b00235

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis and characterization of air-stable cationic mono nitrosonium Fe(I) PNP pincer complexes of the type [Fe(PNP)(NO)Cl](+) are described. These complexes are obtained via direct nitroslyation of [Fe(PNP)Cl-2] with nitric oxide at ambient pressure. On the basis of magnetic and EPR measurements as well as DFT calculations, these compounds were found to adopt a low-spin d(7) configuration and feature a nearly linear bound NO ligand suggesting (FeNO+)-N-I rather than (FeNO center dot)-N-II character. X-ray structures of all nitrosonium Fe(I) PNP complexes are presented. Preliminary investigations reveal that [Fe(PNPNH-iPr)(NO)(Cl](+) efficiently catalyzes the conversion of primary alcohols and aromatic and benzylic amines to yield mono N-alkylated amines in good isolated yields.

引用

页码：4641 / 4646

页数：6

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