Electronic structural changes between nickel(II)-semiquinonato and nickel (III)-catecholato states driven by chemical and physical perturbation

Ohtsu H; Tanaka K

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Electronic structural changes between nickel(II)-semiquinonato and nickel (III)-catecholato states driven by chemical and physical perturbation

机译：化学和物理扰动驱动镍（II）-半喹啉酮和镍（III）-邻苯二酚状态之间的电子结构变化

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The selective synthesis of tetracoordinate square-planar low-spin nickel (II)-semiquinonato (Ni-II-SQ) and nickel (III)-catecholato (Ni-III-Cat) complexes, 1 and 2, respectively, was achieved by using bidentate ligands with modulated nitrogen-donor ability to the nickel ion. The electronic structures of 1 and 2 were revealed by XPS and EPR measurements. The absorption spectra of 1 and 2 in a noncoordinating solvent, dichloromethane (CH2Cl2), are completely different from those in tetrahydrofuran (THF), being a coordinating solvent. As expected from this result, the gradual addition of N,N-dimethylformamide (DMF), which is also a coordinating solvent like THF, into a solution of 1 or 2 in CH2Cl2 leads to dcolor changes from blue (for 1) and brown (for 2) to light green, which is the same color observed for solutions of 1 or 2 in THE Furthermore, the same color changes are induced by varying the temperature. Such spectral changes are attributable to the transformation from square-planar low-spin Ni-II-SQ and Ni-III-Cat complexes to octahedral high-spin Ni-II-SQ ones, caused by the coordination of two solvent molecules to the nickel ion.

机译：通过使用分别完成四坐标方平面低自旋镍（II）-半喹诺酮（Ni-II-SQ）和镍（III）-邻苯二酚（Ni-III-Cat）配合物的选择性合成。具有调节的镍离子氮供体能力的二齿配体。 XPS和EPR测量揭示了1和2的电子结构。非配位溶剂二氯甲烷（CH2Cl2）中1和2的吸收光谱与配位溶剂四氢呋喃（THF）中的吸收光谱完全不同。从该结果可以预料到，将N，N-二甲基甲酰胺（DMF）（也是配位溶剂，如THF）逐渐添加到1或2的CH2Cl2溶液中会导致颜色从蓝色（对于1）和棕色（ 2）变为浅绿色，这与在1或2的溶液中观察到的颜色相同。此外，通过改变温度也会引起相同的颜色变化。这种光谱变化归因于由两个溶剂分子与镍的配位作用引起的从方形平面低自旋Ni-II-SQ和Ni-III-Cat配合物到八面体高自旋Ni-II-SQ的转变。离子。

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来源
《Chemistry: A European journal》 |2005年第11期|共7页
作者
Ohtsu H; Tanaka K;
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正文语种 eng
中图分类化学;
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nickel; redox chemistry; solvatochromism; substituent effects; thermochromism; TRANSITION-METAL COMPLEXES; IMIDAZOLATE-BRIDGED DINUCLEAR; TO-OCTAHEDRAL TRANSFORMATION; O-QUINONE COMPLEXES; VALENCE TAUTOMERISM; SOLID-PHASE; MAGNETIC-PROPERTIES; CRYSTAL-STRUCTURE; LOW-SPIN; CHARGE-DISTRIBUTION;

机译：镍;氧化还原化学;溶剂变色;取代基效应;热致变色;过渡金属配合物;咪唑桥键形结晶;邻相转化;邻苯二酚络合物;价异构;固相;磁性体;晶体;收费分配;

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1. Electronic structural changes between nickel(II)-semiquinonato and nickel (III)-catecholato states driven by chemical and physical perturbation [J] . Ohtsu H, Tanaka K Chemistry: A European journal . 2005,第11期

机译：化学和物理扰动驱动镍（II）-半喹啉酮和镍（III）-邻苯二酚状态之间的电子结构变化
2. Neutral (bis-beta-diketonato) iron(III), cobalt(II), nickel(II), copper(II) and zinc(II) metallocycles: structural, electrochemical and solvent extraction studies [J] . Clegg JK, Bray DJ, Gloe K, Dalton transactions: An international journal of inorganic chemistry . 2007,第17期

机译：中性（bis-beta-diketonato）铁（III），钴（II），镍（II），铜（II）和锌（II）金属环：结构，电化学和溶剂萃取研究
3. Synthesis, structural characterization and electrochemical studies of nickel(II), copper(II) and cobalt(III) complexes of some ONS donor ligands derived from thiosemicarbazide and S-alkyl/aryl dithiocarbazates [J] . Mohammad Akbar Ali, Ai Ling Tan, Aminul Huq Mirza Transition Metal Chemistry . 2012,第7期

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4. Method for determination of nickel (III) and nickel (IV) in alkaline rechargeable nickel cells [C] . Lewis H.L. Battery Conference on Applications and Advances, 1994 . 1994

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Electronic structural changes between nickel(II)-semiquinonato and nickel (III)-catecholato states driven by chemical and physical perturbation

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