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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Selective synthesis,characterization,and configurational flexibility of the coordinatively unsaturated metalcenter of Half-sandwich type complexes with the less-hindered hydrotris(3,5-dimethyl-4-x-1-pyrazolyl)borate ligands [Tp~(Me_2),XM~(II)(k~2-O,O
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Selective synthesis,characterization,and configurational flexibility of the coordinatively unsaturated metalcenter of Half-sandwich type complexes with the less-hindered hydrotris(3,5-dimethyl-4-x-1-pyrazolyl)borate ligands [Tp~(Me_2),XM~(II)(k~2-O,O

机译：具有较少受阻的氢三（3,5-二甲基-4-x-1-吡唑基）硼酸酯配体[Tp〜（Me_2），XM的半三明治型配合物的配位不饱和金属中心的选择性合成，表征和构型灵活性〜（II）（k〜2-O，O

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摘要

The selective synthesis of half-sandwich type complexes of Ni(II) and Co(II) with the less-hindered hydrotris(3,5-dimethyl-4-X)-1-pyrazolyl)borate [X=Me(Tp~(Me_3);a series),H(Tp~(Me);b series),and Br(Tp~(Me_2,Br);c series)]ligands,[Tp~(Me-2,X)M~II(k~2-O,O'-L)][L=NO_3(2),OAc(3)],has been achieved by dropwise addition of aTHF solution of NaTp~(Me_x,X) to an excess amount of ML_2 dissolvedin MeOH.The solid state structures of the nitrato complexes 2 have been charactterized by X-ray crystallography as their solvated form,2solv.(solv.=MeCN,MeOH),in which the metal centers have the six-coordinated cotahedral geometry.Solvates are readily dissociated from the metal center upon dissolution in noncoordinationg solvents,such as CH_2Cl_2 and toluene,as well as drying of a solidsample to give the non-solvatede five-coordinationg solvents,such as CH2Cl_2 and toluene,as well as drying of a solid sample to give the non-solvated five-coordinated species 2.The crystal structure of the non-solvated Tp~(Me)_2Ni derivative 3b~(Ni derivative 3b~(Ni) consists of a highly distorted trigonal bipyramidal nickel center.
机译：Ni（II）和Co（II）的半三明治型配合物与受阻较弱的氢三（3,5-二甲基-4-X）-1-吡唑基）硼酸酯的选择性合成[X = Me（Tp〜（ Me_3）; a系列），H（Tp〜（Me）; b系列）和Br（Tp〜（Me_2，Br）; c系列）]配体，[Tp〜（Me-2，X）M〜II（ k〜2-O，O'-L）] [L = NO_3（2），OAc（3）]，是通过将NaTp〜（Me_x，X）的aTHF溶液滴加到过量的ML_2中而获得的硝酸盐配合物2的固态结构已通过X射线晶体学表征为溶剂化物形式2solv。（solv。= MeCN，MeOH），其中金属中心具有六配位的四面体几何形状。溶于非配位溶剂（如CH_2Cl_2和甲苯）后，很容易从金属中心解离;干燥固体样品，得到非溶剂化的五配位溶剂（如CH2Cl_2和甲苯）;以及干燥固体样品得到非溶剂化的五配位物种2.非溶剂化的Tp〜的晶体结构（Me）_2Ni衍生物3b〜（Ni衍生物3b〜（Ni）由高度扭曲的三角双锥体镍中心组成。

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