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

被引：10
|
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
收藏
页码：4641 / 4646
页数：6
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