Synthesis, Structures, and Properties of a Lantern-type Dinuclear Rhodium(II) Complex cis-[Rh2(4-Me-pf)2(O2CCMe3)2], 4-Me-pf = N,N’-di-p-tolylformamidinate anion
Synthesis, Structures, and Properties of a Lantern-type Dinuclear Rhodium(II) Complex cis-[Rh2(4-Me-pf)2(O2CCMe3)2], 4-Me-pf = N,N’-di-p-tolylformamidinate anion
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灯笼型双核铑(II)配合物顺-[Rh2(4-Me-pf)2(O2CCMe3)2], 4-Me-pf = N,N-di-p-的合成、结构和性能甲苯基甲脒阴离子
DOI：
10.1007/s11696-017-0244-2
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发表时间：
2018
期刊：
影响因子：
2.2
通讯作者：
Yusuke Kataoka
中科院分区：
文献类型：
--
作者：
Makoto Handa;Satoshi Nishiura;Takafumi Masuda;Natsumi Yano;Masahiro Mikuriya;Yusuke Kataoka
灯笼形双核配合物[Rh_2(4-Me-PF)_2(O_2CCF_3)_2](1)(4-Me-PF−=N，N‘-二对甲苯基甲酰胺阴离子)与过量的甲戊酸在氢氧化钠水溶液中与氯仿/甲醇(1：3体积/体积)反应。在室温下搅拌24小时，得到[Rh2(4-Me-PF)2(O2CCMe3)2](2)。用1从乙腈溶液重结晶得到的单晶进行了X-射线晶体结构分析。分析表明，得到的配合物为Acis-[Rh2(4-Me-PF)2(O2CCMe3)2(MeCN)2](2(MeCN)2)，具有灯笼状双核结构，两个甲酰胺和两个羧基配体以Acis-(2：2)方式排列，类似于已报道的1(H2O)2·0.5C6H6和1(MeCN)2的晶体结构。在MeCN中，配合物2在613、506、435和344 nm处有吸收峰，而在MeCN中，配合物1在516、460和326 nm处有吸收峰。通过含时密度泛函理论计算，对1和2的所有谱带进行了合理的分配。此外，还证实了2的羧基上的叔丁基供电子引起了Rh2II、II/Rh2II、III和Rh2II、III/Rh2III、III的氧化还原电位负移(在CH2Cl2中，e1/2=0.32和1.22nV(vs.SCE))，相对于在CH2Cl2上有吸电子氟基团的1(在CH2Cl2中，e1/2=10.71和1.47nV(vs.SCE))。
A lantern-type dinuclear complexcis-[Rh2(4-Me-pf)2(O2CCF3)2] (1) (4-Me-pf−=N,N′-di-p-tolylformamidinate anion) was reacted with an excess of pivalic acid in an aqueous NaOH solution with CHCl3/MeOH (1:3 vol./vol.) at room temperature for 24 h with stirring to givecis-[Rh2(4-Me-pf)2(O2CCMe3)2] (2). A single crystal obtained by recrystallization of1from an acetonitrile solution was employed for X-ray crystal structure analysis. The analysis showed that the obtained complex was acis-[Rh2(4-Me-pf)2(O2CCMe3)2(MeCN)2] (2(MeCN)2) with a lantern-type dinuclear structure and acis-(2:2) arrangement of the two formamidinato and two carboxylato ligands around the dirhodium(II) core, similar to the previously reported crystal structures for1(H2O)2·0.5C6H6and1(MeCN)2. Complex2showed absorption bands at 613, 506, 435, and 344 nm in MeCN, while complex1showed the bands at 516, 460, and 326 nm in MeCN. All the bands observed for1and2were reasonably assigned using time-dependent density functional theory calculation. Moreover, it was confirmed that the electron-donatingt-butyl groups on the carboxylato bridges of2give rise to negative shifts in the redox potentials (E1/2= 0.32 and 1.22 V (vs. SCE) in CH2Cl2) for Rh2II,II/Rh2II,IIIand Rh2II,III/Rh2III,IIIprocesses relative to those of1(E1/2= 0.71 and 1.47 V (vs. SCE) in CH2Cl2) that has electron-withdrawing fluorine groups on the carboxylate bridges.