Elimination of HX (X = Cl, Br) from Haloalkenes on the Ru₂Q₂ (Q = S, Se) Core Complex

Treatment of [{Ru(P(OCH3)3)2(CH3CN)3}2(μ-Q2)](CF3SO3)4 (1, Q = S; 2, Q = Se) with haloalkenes resulted in the formation of complexes carrying unsaturated C3Q2 five-membered or C4Q2 six-membered rings via elimination of HX (X = Cl, Br). The reactions of 1 and 2 with allyl bromide gave the corresponding addition products, (3, Q = S; 4, Q = Se), via elimination of HBr. The elimination process seems to be thermodynamically controlled and takes place at the final stage of the reaction. The steric effect of the halogen atoms seems more operative than the electronic one.将[{Ru(P(OCH3)3)2(CH3CN)3}2(μ-Q2)](CF3SO3)4（配合物1：Q=S；配合物2：Q=Se）与卤代烯烃反应，可通过脱除HX（X=Cl、Br）得到带有不饱和C3Q2五元环或C4Q2六元环的配合物。配合物1与2和烯丙基溴的反应，则通过脱除HBr生成对应的加成产物3（Q=S）与4（Q=Se）。该脱除过程似乎受热力学控制，且发生于反应的最终阶段。卤素原子的空间效应似乎较电子效应更为显著。