Novel lantern-type dinuclear complexes in unusual electronic states with strong π-donor bridging ligands

具有强π供体桥配体的不寻常电子态的新型灯笼型双核配合物

• 批准号: 14540513
• 负责人: EBIHARA Masahiro
• 金额: $ 1.86万
• 依托单位: GIFU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540513/
• 关键词: Ruthenium; Metal-metal bond; Lantern-type complex; Electronic states; Redox potentials; X-ray structure determination; 金属.金属間結合; 磁化率

The reaction of [Ru_2(O_2CMe)_4Cl] with neat 4,5-dimethyl-2-methylaminothiazole (Hdmat) gave an aminothiazolato-bridged paddlewheel Ru_2^<5+> complex, [Ru_2(dmat)_4Cl](1). The corresponding Ru_2^<6+> species, [Ru_2(dmat)_4Cl]PF_6(2), was produced by electrochemical oxidation. Their magnetic susceptibility data of 1.7 and 2.89 BM for 1 and 2 are consistent with the electron configurations of σ^2π^4δ^2π^<*3> and σ^2π^4δ^2π^<*2> for 1 and 2, respectively. The Ru-Ru distances of 1 and 2 are 2.4317(9) and 2.3326(9)Å, respectively. The elongation of the M-M distance on the addition of one electron into a π^* orbital is similar to that observed in a paddlewheele dirhodium complex. The reaction of [Ru_2(O_2CMe)_4Cl] with neat 4-methyl-2-methylaminothiazole (Hmmat) gave [Ru_2(mmat)_4Cl](3) that is very similar to 1. However, the solubility of 3 to common organic solvents are poor. The reaction of 1 with LiCCPh afforded alkylidyne ligated complex [Ru_2(O_2CMe)_4(CCPh)](4). Its Ru-Ru distance is 2.4697(9) Å which is ca.0.03 Å longer than that of 1. Complex 4 is oxidized to Ru_2^<6+> at E_<1/2>=-0.39 V vs Fc^+/Fc which is ca.0.1 V more negative than that of 1.

[Ru_2（O_2CMe）_4Cl]与4，5-二甲基-2-甲氨基噻唑（Hdmat）反应，得到氨基噻唑桥联的轮状钌配合物[Ru_2（dmat）_4Cl]（1）。电化学氧化反应生成了相应的Ru_2^<6+>物种[Ru_2（dmat）_4Cl]PF_6（2）。1和2的磁化率数据分别为1.7和2.89 BM，与1和2的电子组态σ^2π^4δ^2π^<*3>和σ^2π^4δ^2π^<*2>一致。1和2的Ru-Ru距离分别为2.4317（9）和2.3326（9）<$。在π^* 轨道上增加一个电子时，M-M距离的延长与在paddlewheele dirhodium络合物中观察到的相似。[Ru_2（O_2CMe）_4Cl]与纯4-甲基-2-甲氨基噻唑（Hmmat）反应得到与1非常相似的[Ru_2（mmat）_4Cl]（3）。但3对常用有机溶剂的溶解性较差。1与LiCCPh反应，得到亚烷基配位化合物[Ru_2（O_2CMe）_4（CCPh）]（4）。它的Ru-Ru距离为2.4697（9）π，比1长约0.03 π。配合物4在E_<1/2>=-0.39 V（相对于Fc^+/Fc）时被氧化为Ru_2^<6+>，比1负约0.1 V。

项目成果

Masahiro Ebihara: "Diruthenium complexes with aminothiazolato ligand. X-ray and electronic structures of [Ru_2(dmat)_4Cl]^<0/+> (dmat=4,5-dimethyl-2-methylaminothiazolato)"Inorganica Chimica Acta. 351. 305-310 (2003)

Masahiro Ebihara：“与氨基噻唑基配体的二钌配合物。[Ru_2(dmat)_4Cl]^<0/> (dmat=4,5-二甲基-2-甲基氨基噻唑基)的 X 射线和电子结构”Inorganica Chimica Acta。

Masahiro Ebihara, Nobuhiro Nagaya, Naoki Kawashima, Takashi Kawamura: "Diruthenjuin complexes with aminothiazolato ligand. X-ray and electronic structures of [Ru_2(dmat)_4Cl]^<0/+>(dmat=4,5-dimethyl-2-methylaminothiazolato)."Inorganica Chimica Acta. 351.

Masahiro Ebihara、Nobuhiro Nagaya、Naoki Kawashima、Takashi Kawamura：“Diruthenjuin 与氨基噻唑基配体的配合物。[Ru_2(dmat)_4Cl]^<0/ >(dmat=4,5-二甲基-2-甲基氨基噻唑基)的 X 射线和电子结构

Masahiro Ebihara: "Diruthenium complexes with aminothiazolato ligand. X-ray and electronic structures of [Ru_2(dmat)_4Cl]^<0/+>(dmat=4,5-dimethyl-2-methylaminothiazolato)"Inorganica Chimica Acta. (印刷中). (2003)

Masahiro Ebihara：“与氨基噻唑基配体的二钌配合物。[Ru_2(dmat)_4Cl]^<0/+>(dmat=4,5-二甲基-2-甲基氨基噻唑基)的X射线和电子结构”Inorganica Chimica Acta。 ）