First crystal structure determination and high-frequency EPR study of an organoarsanecopper radical complex

Shengfa Ye; Wolfgang Kaim; Biprajit Sarkar; Brigitte Schwederski; Falk Lissner; Thomas Schleid; Carole Duboc-Toia; Jan Fiedler

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First crystal structure determination and high-frequency EPR study of an organoarsanecopper radical complex

机译：有机ar烷铜自由基配合物的首次晶体结构确定和高频EPR研究

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The red radical complex {(mu-bptz)[Cu(AsPh_3)_2]_2}(BF_4) 1,bptz=3,6-bis(2-pyridyl)-1,2,4,5-tetrazine,was obtained as a stable species and characterized by X-ray crystallography,spectroelectrochemistry and EPR at 9.5 and 285 GHz.Comparison with the previously reported {(mu-bptz)[Cu(PPh_3)_2]_2}(BF_4)2 reveals longer Cu-element bonds by about 0.1A but otherwise a similar "organic sandwich" structure involving intramolecualr pi(phenyl)-pi(tetrazine)-pi(phenyl) interactions, a 3+1 coordiantion at the copper (I) centers,and averaged tetrazine intraring bond distances.Reversible oxidation to a blue dication with an intense MLCT band at 650 nm occurs at -0.24V vs.Fc~(+/o).EPR studies show the effect of the higher spin-orbit coupling constant of the As vs.P atoms through slightly larger g anisotropy as determined through high frequency measurements.

机译：获得红色自由基复合物{（mu-bptz）[Cu（AsPh_3）_2] _2}（BF_4）1，bptz = 3,6-双（2-吡啶基）-1,2,4,5-四嗪为是一种稳定的物种，在9.5和285 GHz频率下具有X射线晶体学，光谱电化学和EPR特征。与先前报道的{（mu-bptz）[Cu（PPh_3）_2] _2}（BF_4）2比较，发现更长的Cu-元素键大约0.1A，但其他类似的“有机夹心”结构涉及分子内的pi（苯基）-pi（四嗪）-pi（苯基）相互作用，铜（I）中心的3 + 1配位和四嗪环内平均键距在-0.24V vs.Fc〜（+ / o）时发生可逆氧化为在650 nm处具有很强MLCT谱带的蓝色指示剂.EPR研究表明，As vs.P原子具有更高的自旋轨道耦合常数。通过高频测量确定的较大的g各向异性。

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《Inorganic Chemistry Communications》 |2003年第9期|共5页
作者
Shengfa Ye; Wolfgang Kaim; Biprajit Sarkar; Brigitte Schwederski; Falk Lissner; Thomas Schleid; Carole Duboc-Toia; Jan Fiedler;
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正文语种 eng
中图分类无机化学;
关键词
arsane ligands; copper complex; EPR; pi interaction; radical complex;

机译：rs配体;铜配合物;EPR;π相互作用;自由基配合物;

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机译：有机ar烷铜自由基配合物的首次晶体结构确定和高频EPR研究
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First crystal structure determination and high-frequency EPR study of an organoarsanecopper radical complex

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