REVERSIBLE MULTISTEP AND MULTIELECTRON REDOX BEHAVIOR OF AN OXO-CENTERED TRINUCLEAR RUTHENIUM COMPLEX WITH A REDOX-ACTIVE LIGAND, [RU-3(MU(3)-O)(MU-CH3CO2)(6)(MBPY(+))(3)](4+)(MBPY(+)=N-METHYL-4,4'-BIPYRIDINIUM ION), AND ITS TRIRHODIUM AND DIRUTHENIUM-RHODIUM DERIVATIVES

被引：65

作者：

ABE, M

SASAKI, Y

YAMADA, Y

TSUKAHARA, K

YANO, S

ITO, T

机构：

[1] TOHOKU UNIV, FAC SCI, DEPT CHEM, SENDAI, MIYAGI 98077, JAPAN

[2] HOKKAIDO UNIV, FAC SCI, DEPT CHEM, KITA KU, SAPPORO, HOKKAIDO 060, JAPAN

[3] NARA WOMENS UNIV, FAC SCI, DEPT CHEM, NARA 630, JAPAN

来源：

INORGANIC CHEMISTRY | 1995年 / 34卷 / 17期

关键词：

D O I：

10.1021/ic00121a030

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of new oxo-centered triruthenium, trirhodium, and mixed diruthenium-rhodium complexes having three redox-active terminal ligands, N-methyl-4,4'-bipyridinium ion (mbpy(+)), were prepared: [Ru-3(mu(3)-O)(mu-CH3CO2)(6)(mbpy(+))(3)](PF6)(3) (1), [Ru-3(mu(3)-O)(mu-CH3CO2)(6)(mbpy(+))(3)](PF6)(4) (2), [Ru-3(mu(3)-O)(mu-C6H5CO2)(6)(mbpy(+))(3)](PF6)(ClO4)(3) (3), [Ru2Rh(mu(3)-O)(mu-CH3CO2)(6)(mbpy(+))(3)](ClO4)(4) (4), and [Rh-3(mu(3)-O)(mu-CH3CO2)(6)(mbpy(+))(3)](PF6)(4) (5) Their versatile electrochemical properties were investigated by means of cyclic voltammetry, differential-pulse voltammetry, and controlled-potential absorption spectroscopy. Ru-3 complexes 1 and 2 provide nine-step 11-electron redox waves (involving eight reversible waves) in 0.1 M (n-C4H9)(4)NPF6-CH3CN solution in the range from +2.0 to -3.0 V vs ferrocene/ferrocenium (Fc/Fc(+)) couple at 22 degrees C (M = mol dm(-3)), consisting of five Ru-3(mu(3)-O) core-based one-electron processes at +1.62, +0.64, -0.34, -1.75, and -2.76 V and the terminal ligand-based steps at -1.23, -1.37, -1.99, and -2.09 V. The two couples of terminal ligand-based processes, mbpy(+)/mbpy(.) and mbpy(.)/mbpy(-), split into two steps in 2:1 current intensity ratio. Complex 3 exhibits similar redox behavior. The Ru2Rh complex 4 exhibits eight-step 10-electron redox waves (involving six reversible waves), with the core-based redox processes at +1.65, +0.74, -0.72, and -1.88 V, mbpy(+)/mbpy(.) steps at -1.14, -1.26, and -1.45 V, and mbpy(.)/mbpy(-) steps at -2.14 V (3e). The Rh-3 complex 5 shows two-step four-electron redox behavior with a core-oxidation at +0.97 V and one-step three mbpy(+) reductions at -1.21 V (3e). The splitting of the ligand-based redox waves are caused by the ligand-ligand interactions through an empty d pi-p pi molecular orbital in the trinuclear M(3)(mu(3)-O) framework.

引用

页码：4490 / 4498

页数：9

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