Synthesis, structure and properties of TTF-carboxylate bridged paddlewheel dirhodium complexes, Rh2(ButCO2)3(TTFCO2) and Rh2(ButCO2)2(TTFCO2)2
Synthesis, structure and properties of TTF-carboxylate bridged paddlewheel dirhodium complexes, Rh2(ButCO2)3(TTFCO2) and Rh2(ButCO2)2(TTFCO2)2
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DOI：
10.1016/j.ica.2006.11.024
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发表时间：
2007-05
影响因子：
2.8
通讯作者：
M. Ebihara;Mitsuko Nomura;S. Sakai;T. Kawamura
中科院分区：
文献类型：
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作者：
M. Ebihara;Mitsuko Nomura;S. Sakai;T. Kawamura
四硫富瓦烯甲酸 (TTFCO2H) 与桨轮二铑络合物 Rh2(ButCO2)4 反应生成 TTFCO2 桥络合物 Rh2(ButCO2)3(TTFCO2) (1) 以及顺式和反式-Rh2(ButCO2)2(TTFCO2)2(顺式和反式-2)。通过色谱分离纯化和分离它们的三乙胺加合物[1(NEt3)2]和顺式-[2(NEt3)2]，并通过单晶X射线分析进行表征。反式-[2(NEt3)2]并未从顺式和反式-[2(NEt3)2]的混合物中完全分离，但其单晶是从混合物的溶液中获得的。在 MeCN 中观察到 1 的三步准可逆氧化过程。前两步对应于 TTFCO2 部分的氧化，最后一步对应于 Rh2 核心的氧化。 cis-2 的氧化被观察为一个两步过程，其 E1/2 值与 1 的前两个过程非常相似。室温下 MeCN 中的 1+ 和 cis-22+ 均显示出各向同性 ESR 光谱，两个当量 H 原子的 g 值为 2.008，aH=0.135mT，一个 H 原子的 aH=0.068mT。 cis-2 的氧化还原和 ESR 数据表明 TTF 部分之间的分子内相互作用非常小。
Reaction of tetrathiafulvalene carboxylic acid (TTFCO2H) with paddlewheel dirhodium complex Rh2(ButCO2)4yielded TTFCO2-bridged complexes Rh2(ButCO2)3(TTFCO2) (1) and cis- and trans-Rh2(ButCO2)2(TTFCO2)2(cis- and trans-2). Their triethylamine adducts [1(NEt3)2] and cis-[2(NEt3)2] were purified and isolated with chromatographic separation, and characterized with single crystal X-ray analysis. Trans-[2(NEt3)2] is not completely separated from a mixture of cis- and trans-[2(NEt3)2], but its single crystals were obtained from a solution of the mixture. A three-step quasi-reversible oxidation process was observed for 1 in MeCN. The first two steps correspond to the oxidation of the TTFCO2moiety and the last one is the oxidation of the Rh2core. The oxidation of cis-2 is observed as a two-step process with very similar E1/2values to those of the first two processes for 1. Both 1+and cis-22+in MeCN at room temperature show isotropic ESR spectra with a g value of 2.008 and aH=0.135mT for two equivalent H atoms and aH=0.068mT for one H atom. The redox and ESR data of cis-2 suggest that the intramolecular interaction between the TTF moieties is very small.