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首页> 外文期刊>Chemistry: A European journal >Molecular and Electronic Structure of Four-and Five-Coordinate Cobalt Complexes Containing Two o-Phenylenediamine-or Two o-Aminophenol-Type Ligands at Various Oxidation Levels:An Experimental,Density Functional,and Correlated ab initio Study
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Molecular and Electronic Structure of Four-and Five-Coordinate Cobalt Complexes Containing Two o-Phenylenediamine-or Two o-Aminophenol-Type Ligands at Various Oxidation Levels:An Experimental,Density Functional,and Correlated ab initio Study

机译：含两个氧化水平的两个邻苯二甲胺或两个邻氨基苯酚型配体的四配位和五配位钴配合物的分子和电子结构：实验，密度泛函和相关的从头算研究

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摘要

The bidentate ligands N-phenyl-o-phenylenediamine,H_2(2L^),or its analogue 2-(2-trifluoromethyl)-anilino-4,6-di-rert-butylphenol,(4L'o),react with[Con(CH_3Co_2)_2]-4H_2O and triethylamine in acetonitrile in the presence of air yielding the square-planar,four-coordinate species[Co(2LN)_2](1)and[Co(4L0)_2](4)with an S=l/2 ground state.The corresponding nickel complexes[Ni(4L0)_2](8)and its cobaltocene reduced form[Com(Cp)_2][Ni(4L0)_2](9)have also been synthesized.The five-coordinate species[Co(2LN)_2(fBu-py)](2)(S = fy and its one-electron oxidized forms[Co(2LN)_2(fBu-py)](O_2CCH_3)(2 a)or[Co(2LN)_2I](3)with diamagnetic ground states(5 = 0)have been prepared,as has the species[Co-(4L0)_2(CH_2CN)](7).The one-electron reduced form of 4,namely[Co(Cp)_2][Co(4L0)_2](5)has been generated through the reduction of 4 with[Co(Cp)_2].Complexes 1,2,2 a,3,4,5,7,8,and 9 have been characterized by X-ray crystallography(100 K).The ligands are non-innocent and may exist as catecholate-like dianions(2Ljf)_2~,(4Lo)_2~ or it-radical semiquinonate monoanions(2L￡°r,(4-L^°)-or as neutral benzoquinones(2L{fQ)°,(4Lj^Q)°;the spectroscopic oxidation states of the central metal ions vary accordingly.Electronic absorption,magnetic circular dichroism,and EPR spec-troscopy,as well as variable tempera-ture magnetic susceptibility measurements have been used to experimentally determine the electronic structures of these complexes.Density functional theoretical(DFT)and correlated ab initio calculation have been performed on the neutral and monoanionic species[Co(1LN)_2]0'~ in order to understand the structural and spectroscopic properties of complexes.It is shown that the corresponding nickel complexes 8 and 9 contain a low-spin nick-el(n)ion regardless of the oxidation level of the ligand,whereas for the corresponding cobalt complexes the situation is more complicated.Spectroscopic oxidation states describing a d6(Co111)or d7(Co11)electron configuration cannot be unambiguously assigned.
机译：双齿配体N-苯基-邻-苯二胺，H_2（2L ^），或其类似物2-（2-三氟甲基）-苯胺基-4,6-二-叔丁基苯酚，（4L'o），与[Con在空气中在乙腈中的（CH_3Co_2）_2] -4H_2O和三乙胺产生带有S的方形，四配位物质[Co（2LN）_2]（1）和[Co（4L0）_2]（4） = l / 2基态。还合成了相应的镍配合物[Ni（4L0）_2]（8）及其钴还原形式[Com（Cp）_2] [Ni（4L0）_2]（9）。这五个坐标物质[Co（2LN）_2（fBu-py）]（2）（S = fy及其单电子氧化形式[Co（2LN）_2（fBu-py）]（O_2CCH_3）（2 a）or [制备了具有反磁性基态（5 = 0）的Co（2LN）_2I]（3），以及[Co-（4L0）_2（CH_2CN）]（7）物种。4的单电子还原形式4即通过[Co（Cp）_2]还原4生成了[Co（Cp）_2] [Co（4L0）_2]（5）。络合物1,2,2 a，3,4,5,7 ，8和9已通过X射线晶体学（100 K）进行了表征。这些配体是非无毒的，并且可能以儿茶酚类二价阴离子的形式存在（2Ljf ）_2〜，（4Lo）_2〜或自由基半奎宁酸单阴离子（2L ￡°r，（4-L ^°）-或作为中性苯醌（2L {fQ）°，（4Lj ^ Q）°;光谱氧化中心电子离子的状态也相应地变化。电子吸收，磁性圆二色性和EPR光谱以及可变温度磁化率测量已用于通过实验确定这些配合物的电子结构。密度泛函理论（DFT） ）和相关的从头算法已经对中性和单阴离子物质[Co（1LN）_2] 0'〜进行了计算，以了解络合物的结构和光谱性质。结果表明，相应的镍络合物8和9包含一个不论配体的氧化程度如何，均会产生低自旋的nickel-el（n）离子，而对于相应的钴络合物而言，情况则更为复杂。描述d6（Co111）或d7（Co11）电子构型的光谱氧化态不能明确已分配。

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