Synthesis, Characterization, and Redox Behavior of Mixed 1,3-Diyne Dicobalt/Triosmium and Dicobalt/Triruthenium Carbonyl Clusters
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- 作者：Consuelo Moreno ; Marí ; a-Luisa Marcos ; Marí ; a-José ; Macazaga ; Javier Gó ; mez-Gonzá ; lez ; Raquel Gracia ; Fernando Benito-Ló ; pez ; Esther Martí ; nez-Gimeno ; Avelina
- 刊名：Organometallics
- 出版年：2007
- 出版时间：October 8, 2007
- 年：2007
- 卷：26
- 期：21
- 页码：5199 - 5208
- 全文大小：361K
- 年卷期：v.26,no.21(October 8, 2007)
- ISSN：1520-6041
文摘
The reaction between [Co2(-2-HCCC2SiMe3)(-dmpm)(CO)4] (1) and [Os3(CO)10(MeCN)2] givesrise to the formation of three new products: [Os3(-H){3-1:2;-2-C2C2SiMe3[Co2(-dmpm)(CO)4]}(CO)9] (3), [Os3(-H){-1;-2-C2C2SiMe3[Co2(-dmpm)(CO)4]}(CO)10] (4), and [Os3{3-1:2;-2-HC2C2SiMe3[Co2(-dmpm)(CO)4]}(-CO)(CO)9] (5). These complexes adopt three different coordinationmodes: 3-2 perpendicular, -1 edge-bridged, and 3-2 parallel mode, respectively. When the reactionis carried out with [Ru3(CO)12], only one product is obtained, [Ru3(-H){3-1:2;-2-C2C2SiMe3[Co2(-dmpm)(CO)4]}(CO)9] (6), in which the triruthenium cluster is coordinated in a perpendicular mode.However, the reaction of [Co2(-2-HC2(CC)2C2SiMe3)(-dppm)(CO)4] (2), stericaly more congested,with [Os3(CO)10(Me3CN)2] yields only one product, the edge-bridged-coordinated [Os3(-H){-1;-2-C2C2SiMe3[Co2(-dppm)(CO)4]}(CO)10] (7). [Os3(CO)10(MeCN)2] reacts with HCCSiMe3, giving riseto the known parallel and perpendicular complexes and the new edge-bridged [Os3(-H){-1-C2SiMe3(CO)10]. All products were characterized by analytical and spectroscopic data (IR, 1H, 13C, and 31P NMR,and MS). Crystals of 3, 6, and 7 suitable for single-crystal X-ray diffraction were grown, and the molecularstructures of these compounds are discussed. A comparative electrochemical study of all these complexesis presented by means of the cyclic and square-wave voltammetry techniques.