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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Kinetic evidence of ring closure step in the substitution of cis-[Cr(bpy)_2(OH_2)_2]~(3+) with [M(CN)_8]~(4-) (M = Mo, W)
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Kinetic evidence of ring closure step in the substitution of cis-[Cr(bpy)_2(OH_2)_2]~(3+) with [M(CN)_8]~(4-) (M = Mo, W)

机译:用[M(CN)_8]〜(4-)取代顺式[Cr(bpy)_2(OH_2)_2]〜(3+)的闭环步骤的动力学证据(M = Mo,W)

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摘要

The substitution rtaction of' cis-[Cr(bpy)2(6H2)2]3 + with [M(CN)8r- (M = Mo, W) results in the fonnation of {[(bpy)2Cr(v- NC)2M(CN)6]} -, The new species exhibit intense MMct transitions and a high degree of. electronic coupling revealing a 1 borderline localized-to-delocalized class of behavior. The complex formation reactions were studied as a function of [M(CN)s]4 - concentration, pH and temperature. Two consecutive reaction steps were observe<;!: the first exhibits dependence on the [M(CN)s]4- concentration and the second is concentration-independent. The mechanism has been rational.ized in terms of an ion-pair formation preceding two successive anation steps: initial attachment of the N-end of the cyano ligand of the octacyanometalate moiety followed by slower intramolecular binding of the other N-site leading to ring closure. The large positive t.H.. and large and negative ~S.. values for the second step suggest associative'character of the substitution reaction.
机译:'顺式[[Cr(bpy)2(6H2)2] 3 +与[M(CN)8r-(M = Mo,W)的取代反应导致形成{[((bpy)2Cr(v- NC) )2M(CN)6]}-,新物种展现出强烈的MMct过渡和高度的MMct过渡。电子耦合揭示了1种边界局部化到非局部化的行为。研究了复合物形成反应与[M(CN)s] 4-浓度,pH和温度的关系。观察到两个连续的反应步骤:;第一个显示出对[M(CN)s] 4-浓度的依赖性,第二个显示出与浓度无关。就在两个连续的阳离子化步骤之前形成离子对而言,该机理已得到合理化:十八酸金属盐部分的氰基配体的N端初始连接,随后较慢的分子内分子间结合导致环化关闭。第二步的较大的正t.H ..和较大的及负的〜S ..值表明取代反应具有“关联”特征。

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