1-苯基-3-(吡啶-2-基)苯并[e][1,2,4]三嗪基：配位化学的第一个“布拉特自由基”。

1-Phenyl-3-(pyrid-2-yl)benzo[e][1,2,4]triazinyl: the first "Blatter radical" for coordination chemistry.

机构信息

Department of Chemistry, University of Jyväskylä , P.O. Box 35, FI-40014 Jyväskylä, Finland.

出版信息

Inorg Chem. 2014 Jan 6;53(1):33-5. doi: 10.1021/ic402954p. Epub 2013 Dec 12.

Abstract

A neutral air- and moisture-stable N,N'-chelating radical ligand, 1-phenyl-3-(pyrid-2-yl)benzo[e][1,2,4]triazinyl (1) was synthesized and characterized by electron paramagnetic resonance spectroscopy, X-ray crystallography, and magnetic measurements. Subsequent reaction of 1 with Cu(hfac)2·2H2O (hfac = hexafluoroacetylacetonate) under ambient conditions afforded the coordination complex Cu(1)(hfac)2 in which the radical binds to the metal in a bidentate fashion. Magnetic susceptibility data collected from 1.8 to 300 K indicate a strong ferromagnetic metal-radical interaction in the complex and weak antiferromagnetic radical···radical interactions between the Cu(1)(hfac)2 units. Detailed computational investigations support this assignment. Radical 1 is a new addition to the growing library of 1,2,4-triazinyl radicals and the first member of this family of paramagnetic species synthesized specifically for coordination purposes.

摘要

一种中性的空气和水分稳定的 N,N'-螯合自由基配体，1-苯基-3-(吡啶-2-基)苯并[e][1,2,4]三嗪基（1）被合成并通过电子顺磁共振波谱、X 射线晶体学和磁性测量进行了表征。随后，在环境条件下，1 与 Cu(hfac)2·2H2O（hfac = 六氟乙酰丙酮）反应，得到配位复合物 Cu(1)(hfac)2，其中自由基以双齿配位的方式与金属结合。在 1.8 到 300 K 之间收集的磁化率数据表明，该配合物中存在强烈的铁磁金属-自由基相互作用，以及 Cu(1)(hfac)2 单元之间较弱的反铁磁自由基···自由基相互作用。详细的计算研究支持了这一分配。自由基 1 是不断增长的 1,2,4-三嗪基自由基库中的一个新成员，也是为配位目的专门合成的该家族顺磁物种中的第一个成员。