Laromaine Anna, Teixidor Francesc, Kivekäs Raikko, Sillanpää Reijo, Arca Massimiliano, Lippolis Vito, Crespo Eulàlia, Viñas Clara
Institut de Ciència de Materials de Barcelona, Campus U.A.B., 08193 Bellaterra, Spain.
Dalton Trans. 2006 Nov 28(44):5240-7. doi: 10.1039/b610944f. Epub 2006 Oct 5.
Reaction of the lithium salt Li[1-R-1,2-closo-C(2)B(10)H(10)] with selenium under mild conditions, followed by hydrolysis gave the diselenide compound (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) in contrast to the well-reported mercapto compounds 1-SH-2-R-1,2-closo-C(2)B(10)H(10) obtained using a similar synthetic procedure. Details for the preparation and X-ray structural characterisation of the new compounds (2-Me-1,2-closo-C(2)B(10)H(10))(2)Se, (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) (R = Me, Ph, ) are specified. To further explore the mechanism of the dimerization reaction, the complex [Au(1-Se-2-Me-1,2-closo-C(2)B(10)H(10))(PPh(3))] was synthesized, confirming the existence of the intermediate Li[1-Se-2-R-1,2-closo-C(2)B(10)H(10)] at the early stages of the reaction before selenium oxidation. Theoretical calculations and cyclic voltammetry (CV) studies were carried out to compare the bonding nature of the sulfur and the selenium analog compounds. It was determined that diselenides have a higher tendency to reduce with respect to the disulfides and all chalcogen atoms were found to be positively charged.
在温和条件下，锂盐Li[1-R-1,2-闭式-C₂B₁₀H₁₀]与硒反应，随后水解得到二硒化物化合物(1-Se-2-R-1,2-闭式-C₂B₁₀H₁₀)₂，这与使用类似合成方法得到的大量报道的巯基化合物1-SH-2-R-1,2-闭式-C₂B₁₀H₁₀形成对比。详细说明了新化合物(2-Me-1,2-闭式-C₂B₁₀H₁₀)₂Se、(1-Se-2-R-1,2-闭式-C₂B₁₀H₁₀)₂(R = Me、Ph等)的制备和X射线结构表征。为了进一步探索二聚反应的机理，合成了配合物[Au(1-Se-2-Me-1,2-闭式-C₂B₁₀H₁₀)(PPh₃)]，证实了在硒氧化之前反应早期中间体Li[1-Se-2-R-1,2-闭式-C₂B₁₀H₁₀]的存在。进行了理论计算和循环伏安法(CV)研究以比较硫和硒类似化合物的键合性质。确定相对于二硫化物，二硒化物具有更高的还原倾向，并且发现所有硫族原子都带正电荷。
