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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >V ~(IV)O and Cu ~(II) complexation by ligands based on pyridine nitrogen donors
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V ~(IV)O and Cu ~(II) complexation by ligands based on pyridine nitrogen donors

机译：基于吡啶氮供体的配体的V〜（IV）O和Cu〜（II）络合

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摘要

The binary and ternary systems formed by V ~(IV)O and Cu ~(II) ions with ligands (L) based on the pyridine ring (1,10-phenanthroline (phen), 2,2′-bipyridine (bpy), 2,2′:6′, 2′′-terpyridine (terpy), 2,2′-bipyrimidine (bpm) and 2,3-bis(2-pyridyl)pyrazine (bpp)) were studied, combining spectroscopic (EPR and UV-vis), pH-potentiometric and computational (DFT calculations) methods. In the systems with V ~(IV)O, the formation of mono-chelated complexes with equatorial-equatorial and equatorial-axial (phen, bpy, bpm and bpp) or equatorial-equatorial-equatorial and equatorial-axial-equatorial coordination (terpy) and bis-chelated species with cis-octahedral geometry, with a water or a hydroxido ion in the fourth equatorial position, is demonstrated. Phen, bpy, bpm and bpp form also a dinuclear [(VO) _2L _2(H _2O) _2(OH) _2] ~(2+) complex with an anti-coplanar arrangement of the two V ~(IV)O ions and a ferromagnetic coupling between the metal ions. Due to the low basicity of the nitrogen donors, the potentially tetradentate 2,2′-bipyrimidine and 2,3-bis(2-pyridyl) pyrazine behave like simple bidentate ligands, and in the ternary systems with 2,2′-bipyridine the expected dinuclear species, in which the former ligands would act as a bridge between the two metal ions using all four nitrogen donors, are not formed. The interaction of phen and Cu ~(II)-phen complexes with human serum albumin (HSA) was also studied at pH 7.4 by circular dichroism and EPR spectroscopy, the formation of several HSA-Cu ~(II)-phen containing species being confirmed and their binding constants determined.
机译：由V〜（IV）O和Cu〜（II）离子与基于吡啶环的配体（L）形成的二元和三元系统（1,10-菲咯啉（phen），2,2'-联吡啶（bpy），研究了2,2'：6'，2''-吡啶（terpy），2,2'-联嘧啶（bpm）和2,3-双（2-吡啶基）吡嗪（bpp）），结合光谱（EPR和紫外可见），pH电位和计算（DFT计算）方法。在具有V〜（IV）O的系统中，形成具有赤道-赤道和赤道-轴向（phen，bpy，bpm和bpp）或赤道-赤道-赤道和赤道-轴向-赤道配位的单螯合配合物（叔丁基）和具有顺八面体几何形状的双螯合物种，其中在第四赤道位置具有水或氢氧根离子。苯酚，bpy，bpm和bpp还会形成双核[（VO）_2L _2（H _2O）_2（OH）_2]〜（2+）络合物，其中两个V〜（IV）O离子呈反共面排列，金属离子之间的铁磁耦合。由于氮供体的碱性较低，潜在的四齿2,2'-联嘧啶和2,3-双（2-吡啶基）吡嗪的行为就像简单的双齿配体，在三元体系中带有2,2'-联吡啶的没有形成预期的双核物种，其中使用所有四个氮供体，前者的配体将充当两种金属离子之间的桥梁。还通过循环二色性和EPR光谱研究了pH 7.4下phen和Cu〜（II）-phen配合物与人血清白蛋白（HSA）的相互作用，证实了几种含HSA-Cu〜（II）-phen的物种的形成并确定它们的结合常数。

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