Valence Fluctionality of Trinuclear Ruthenium Complex Dimers

三核钌配合物二聚体的价态波动性

基本信息

批准号：
09044054
负责人：
ITO Tasuku
金额：
$ 3.14万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for international Scientific Research
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

lntramolecular electron transfers within the mixed valence states of the ligand bridged hexaruthenium clusters Ru_3(mu_3-O)(mu-CH_3CO_2)_6(CO)(L)(mu-L')Ru_3(mu_3-O)(mu-CH_3CO_2)_6(CO)(L)(L' = 1,4-pyrazine ; L = 4-dimethyl-aminopyridine (1), pyridine (2), 4-cyanopyridine (3), or L' = 4,4'-bipyridine ; L = 4-dimethyl-aminopyridine (4), pyridine (5), 4-cyanopyridine (6) were examined. Two discrete and reversible single electron reductions are evident by cyclic voltammetry in the redox chemistry of 1 - 5, and the inter-cluster charge transfer complexes are well defined. The splitting of the reduction waves, E, is related to the electronic coupling H_<AB> between the triruthenium clusters, and varies from 80 mV for 5 to 440 mV for 1. In the case of 6, the splitting of the reduction waves, E, is < 50 mV and the inter-cluster charge transfer complex is not defined. The mixed valence states of 1 - 3 also exhibit intervalence charge transfer (ICT) bands in the region 12,100 cm^<-1> (1) to 10,80 … More 0 cm^<-1> (3) which provide spectroscopic estimates of H_<AB> in the range 2180 cm^<-1> (1) to 1310 cm^<-1> (3). The magnitude of the electronic coupling H_<AB> is found to strongly influence the IR spectra of the singly reduced (-1) mixed valence states of 1 - 6 in the n(CO) region. In the case of relatively weak electronic coupling (4 - 6), two v(CO) bands are clearly resolved. In the cases of strong electronic coupling (1 - 3), these bands broaden to a single v(CO) absorption band. These data allow the rate constants, kappa_c, for electron transfer in the mixed valence states of 1, 2, and 3 to be estimated by simulating dynamical effects (Bloch type equations) on v(CO) absorption bandshape at 9 x 10^<11> s^<-1>, 5 x l0^<11> s^<-1>, and ca . 1 x 10^<11> s^<-1>, respectively. The less strongly coupled 4,4'-bipyridine bridged complexes 4 - 6 exhibit IR lineshapes in the -1 mixed valence states that are not as strongly affected by electron transfer dynamics. The rate constant for the -1 mixed valence state of 4 is close to the lower limit that can be estimated by this approach, between 1 x 10^<10> and 1 x 10^<11> s^<-1>. Less

lntramolecular电子传输，具有配体的混合价值的六边形链状簇L）（mu-l'）ru_3（mu_3-o）（mu-ch_3co_2）_6（CO） 4-二甲基 - 氨基吡啶（1），吡啶（2），4-氰基吡啶（3）或L'= 4,4' - 二吡啶检查了两个离散的和可逆的电子还原，在1-5的氧化还原化学中，c YCLICENTIMET和组合中心的Trex均得到很好的定义。 440 mV对于1。在6的情况下，重新分裂e，<50 mV，群间电荷转移率complence Comp。 >（1）至10,80…更多0 cm^<-1>（3），在2180 cm^<-1>（1）至1310 cm^<1>（（ 3）单个V（CO）吸收频段。 10^<11> S^<-1>，5 x L0^<11> s^<-1>，Ca。 -1由电子转移动力学强烈影响4的混合价。 >少

项目成果

期刊论文数量（10）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

伊藤翼: "Effects of Rapid Intramolecular Electron Transfer on Vibrationl Spectra." Science. 277. 660-663 (1997)

伊藤翼：“快速分子内电子转移对振动光谱的影响。”277. 660-663 (1997)

DOI：
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0
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通讯作者：

Ken-ichiro Ota, Hirokazu Sasaki, Taeko Matsui, Tomohiko Hamaguchi, Tadashi Yamaguchi, Tasuku Ito, Hiroaki Kido, and Clifford P.Kubiak: "Syntheses and Properties of a Series of Oxo-Centered Triruthenium Complexes and Their Bridged Dimers with Isocyanide Li

Ken-ichiro Ota、Hirokazu Sasaki、Taeko Matsui、Tomohiko Hamaguchi、Tadashi Yamaguchi、Tasuku Ito、Hiroaki Kido 和 Clifford P.Kubiak：“一系列氧中心三钌配合物及其与异氰化物 Li 的桥联二聚体的合成和性质

DOI：
发表时间：
期刊：
影响因子：
0
作者：
通讯作者：

Tasuku Ito, Tomohiko Hamaguchi, Haruko Nagino, Tadashi Yamaguchi, Hiroaki Kido, Igor S.Zavarine, Todd Richmond, John Washington, and Clifford P.Kubiak: "Electron Transfer on the Infrared Vibrational Time Scale in the Mixed Valence State of 1,4-Pyrazine an

Tasuku Ito、Tomohiko Hamaguchi、Haruko Nagino、Tadashi Yamaguchi、Hiroaki Kido、Igor S.Zavarine、Todd Richmond、John Washington 和 Clifford P.Kubiak：“1,4 混合价态红外振动时标上的电子转移