单体靶物双(乙酰丙酮)铜(II)与转金属物双(二氧基二硫代磷酸)锌(II)在二氯甲烷中的反应产物及动力学

H. Abo-Eldahab
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引用次数: 0

摘要

双-(乙酰丙酮)铜(ΙΙ) (A)与转金属剂Zn((EtO)2PS2)2 (B2)的反应Et =乙基)在二氯甲烷中的反应是一个简单的、不可逆的、在宽温度范围内进行的二级反应,这是单核靶a与金属变性物二级反应的第一个例子。kobsd与[A]呈线性关系,即在最慢反应步骤的活化配合物中有一个A和一个B2。最慢的一步是前体的形成,因为B2是一种非常弱的复合体。A/B2反应的产物是强后继络合物Zn(acac)2•Cu(ps)2。并与同一目标(A)与s -甲基异丙基肼碳二硫代-碳二硫代-金属(II)配合物M(SN)2 (M=Ni (C1)和Zn (C2))反应的数据进行了比较。该反应不像A与Ni ((MeO)2PS2)2 (B1)的反应;Me=甲基),因为它是不可逆的,也与测量到的B2相对于B1较低的相对热力学稳定性相一致。
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Products and Kinetics of the Reaction of Monomeric Target Bis-(Acetylacetonato) Copper(II) with Transmetalator Bis-(Diethoxydithiophosphato) Zinc(II) in Methylene Chloride
Reaction of bis-(acetylacetonato) copper(ΙΙ) (A) with transmetalator Zn((EtO)2PS2)2 (B2; Et = ethyl) in methylene chloride is a simple irreversible second-order process over a wide temperature range which is the first example of a second-order reaction of mononuclear target A with a transmetalator. The plots of kobsd vs [A] are linear, meaning that there is one A and one B2 in the activated complex of the slowest reaction step. The slowest step is precursor formation on the basis that B2 is an exceptionally weak complex. The product of the A/B2 reaction is the strong successor complex Zn(acac)2•Cu(ps)2. The data are compared with those for reactions of the same target (A) with S-methyle isopropylidenehydrazinecarbodithioate-carbodithioato-metal(II) complexes M(SN)2 (M=Ni (C1) and Zn (C2)). The reaction is not like that of A with Ni ((MeO)2PS2)2 (B1; Me=methyl), because it is irreversible and also consistent with the measured lower relative thermodynamic stability of B2 compared to B1.
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