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Cyclometallation on platinum(II) complexes; the role of the solvent and added base donor capability on the reaction mechanisms

机译:铂(II)配合物上的环金属化;溶剂的作用和增加的碱给体能力对反应机理的影响

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The reaction of PhCH = NCH_2CH_2NMe_2 with [PtCl_2S_2](S = SMe_2 or dmso) produces [PtCl_2(PhCH = NCH_2CH_2NMe_2)](1) in which the imine acts as a bidentate [N,N'] ligand. The cyclometallated [C,N,N'] platinum(II) complex [PtCl_2(C_6H_4CH = NCH_2CH_2NMe_2)] (2) has been obtained by refluxing a methanol solution of complex 1 in the presence of base; both complexes 1 and 2 have been characterized crystalloraphical. The cyclometallation process has been studied kinetically at variable temperature and pressure as a function of the base added in methanol and ethanol solutions. In all cases, the actual C-H bond activation is preceded by the Z to E isomerization of the imine; detection of this species by proton NMR has also been achieved. The kinetic, thermal and baric activation parameters associated with the two processes are indicative of a different reaction mechanism operating for the reactions when the "external" base added (NaCH_3CO_2) can, in fact, react with the starting material to form a new acetato complex which allows for the reactions to be intramolecular.
机译:PhCH = NCH_2CH_2NMe_2与[PtCl_2S_2](S = SMe_2或dmso)的反应产生[PtCl_2(PhCH = NCH_2CH_2NMe_2)](1),其中亚胺充当双齿[N,N']配体。环金属化的[C,N,N']铂(II)配合物[PtCl_2(C_6H_4CH = NCH_2CH_2NMe_2)](2)是在碱存在下,将配合物1的甲醇溶液回流得到的。配合物1和2均已表征为晶体。已经在可变温度和压力下动力学研究了环金属化过程,该过程是在甲醇和乙醇溶液中添加碱的函数。在所有情况下,实际的C-H键激活之前都是亚胺的Z到E异构化;通过质子NMR检测该物质也已经实现。当添加的“外部”碱(NaCH_3CO_2)实际上可以与起始原料反应形成新的acetato配合物时,与这两个过程相关的动力学,热和重活化参数表明反应的反应机理不同。这使得反应可以在分子内进行。

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