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一种新型N3O供体螯合配体的锰(II)化学:溶剂和草酸盐结合配合物的合成、X射线结构及磁性

Manganese(II) chemistry of a new N3O-donor chelate ligand: synthesis, X-ray structures, and magnetic properties of solvent- and oxalate-bound complexes.

作者信息

Fuller Amy L, Watkins Rex W, Dunbar Kim R, Prosvirin Andrey V, Arif Atta M, Berreau Lisa M

机构信息

Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322-0300, USA.

出版信息

Dalton Trans. 2005 Jun 7(11):1891-6. doi: 10.1039/b500534e. Epub 2005 Apr 28.

Abstract

The synthesis and characterization of a new N3O donor ligand N-benzyl-N-((6-pivaloylamido-2-pyridyl)methyl)-N-(2-pyridylmethyl)amine (bpppa) is reported. Treatment of bpppa with Mn(II)(ClO4)2.6H2O in acetonitrile solution yielded the mononuclear (bpppa)Mn(CH3CN)(H2O)2 (1) which was characterized by X-ray crystallography, elemental analysis, IR spectroscopy, mass spectrometry, and a solution magnetic moment measurement. Admixture of equimolar equivalents of bpppa and Mn(II)(ClO4)2.6H2O in methanol solution, followed by addition of 0.5 or 1 equivalents of sodium oxalate, yielded the binuclear complex {(bpppa)Mn}2([mu]-C2O4)2 (2), which was characterized by X-ray crystallography, elemental analysis, IR spectroscopy, mass spectrometry, and solid-state magnetic measurements. While 1 is mononuclear, the formation of the binuclear oxalate derivative indicates that use of the bpppa ligand does not enable isolation of a complex that is structurally relevant to a proposed 1:1 Mn(II)-oxalate adduct in the catalytic cycle of the oxalate degrading enzyme oxalate decarboxylase.

摘要

报道了一种新型N3O供体配体N-苄基-N-((6-新戊酰氨基-2-吡啶基)甲基)-N-(2-吡啶基甲基)胺(bpppa)的合成与表征。在乙腈溶液中,bpppa与Mn(II)(ClO4)2·6H2O反应生成单核配合物(bpppa)Mn(CH3CN)(H2O)2 (1),通过X射线晶体学、元素分析、红外光谱、质谱和溶液磁矩测量对其进行了表征。在甲醇溶液中,将等摩尔当量的bpppa和Mn(II)(ClO4)2·6H2O混合,然后加入0.5或1当量的草酸钠,得到双核配合物{(bpppa)Mn}2(μ-C2O4)2 (2),通过X射线晶体学、元素分析、红外光谱、质谱和固态磁测量对其进行了表征。虽然1是单核的,但双核草酸盐衍生物的形成表明,使用bpppa配体并不能分离出与草酸盐降解酶草酸脱羧酶催化循环中提出的1:1 Mn(II)-草酸盐加合物结构相关的配合物。

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