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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Multimetallic Complex Composed of Redox-Active Bridging Quinonediimine Ligand
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Multimetallic Complex Composed of Redox-Active Bridging Quinonediimine Ligand

机译：氧化还原活性桥醌二胺配体组成的多金属配合物

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摘要

A pi-conjugated quinonediimine ligand possessing two terminal redox-active ferrocenyl groups, N,N'-bis{(4'-ferrocenylcarboxamide)phenyl}-1,4- benzoquinonediimine (L_ox), was synthesized. The quinonediimine ligand L_ox was reduced to L_(red) composed of the phenylenediamine moiety on treatment with hydrazine hydrate. The reaction of L_(ox) with the palladium(II) complex 1 bearing the N,N'-bis(2-phenylethyl)-2,6-pyridinedicarboxamide ligand afforded the multimetallic complex 2. Variable temperature ~1H NMR studies of 2 indicated the existence of syn and anti isomers, in which the anti isomer is enthalpically more favorable than the syn isomer in CD_2Cl_2 by 0.9 kcal mol~(-1), but entropically less favorable by 2.6 cal mol~(-1) k~(-1) from the van't Hoff plot. The redox function of the quinonediimine moiety is modulated by complexation with 1. The complex 2 showed three separate redox waves, which are assignable to the successive one-electron reduction of the quinonediimine moiety and oxidation of the two terminal ferrocenyl groups. Chemical reduction of 2 in CH_2Cl_2 with [Co(Cp)_2] resulted in the appearance of ESR signals with weak ~(105)Pd coupling centered around g=2.004. The unpaired electron appears to locate mostly on the quinonediimine moiety with some delocalization onto the palladium center.
机译：合成具有两个末端氧化还原活性二茂铁基团的N，N'-双{（4'-二茂铁基羧酰胺）苯基} -1,4-苯并醌二亚胺（L_ox）的π-共轭醌二亚胺配体。在用水合肼处理时，将醌二亚胺配体L_ox还原为由苯二胺部分组成的L_（红色）。 L_（ox）与带有N，N'-双（2-苯基乙基）-2,6-吡啶二甲酰胺配体的钯（II）配合物1的反应提供了多金属配合物2。表明1的可变温度〜1H NMR研究顺式和反式异构体的存在，其中在CD_2Cl_2中，反式异构体在焓上比顺式异构体好0.9 kcal mol〜（-1），而在熵上不如2.6 cal mol〜（-1）k〜（- 1）从范霍夫图。醌二亚胺部分的氧化还原功能通过与1的络合来调节。配合物2显示三个单独的氧化还原波，这可归因于醌二亚胺部分的连续单电子还原和两个末端二茂铁基团的氧化。用[Co（Cp）_2]在CH_2Cl_2中化学还原2导致出现ESR信号，其〜（105）Pd耦合弱，中心为g = 2.004。未配对的电子似乎主要位于奎宁二胺部分上，并且在钯中心上有一些离域。

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