h3)][PF6] (1) with p-XC6H4C⋮CH (X = H, Cl) yields the transient and observable vinylidene species [Ru(η5-C9H7)κ1(P)-PPh2(CH2CHCH2)}(PPh3)(CCH(p-XC6H4))]+, which react further by an intramolecular [2 + 2] cycloaddition process, forming bicyclic alkylidene compounds. The formation of the vinylidene intermediates, associated with a change of the binding mode of the allylphosphine ligand from κ3(P,C,C)
复杂的[Ru(η的反应5 -C 9 ħ 7)κ 3(P,C,C)-PPh 2(CH 2 CH CH 2)}(PPH 3)] [PF 6 ](1)与p -XC 6 ħ 4 ç⋮CH(X = H,Cl)的产生瞬态和可观察到的偏二种的[Ru(η 5 -C 9 ħ 7)κ 1(P)-PPh 2(CH 2 CH CH 2) }(PPh 3)(C CH(p -XC 6 H 4))] +,它们通过分子内[2 + 2]环加成反应进一步反应,形成双环亚烷基化合物。偏二中间体的形成,与从所述κallylphosphine
配体结合模式的改变相关联的3(P , Ç , C),以单齿κ 1(P)的协调,已经通过动力学测量研究了
氯仿进行d在38°C下。一阶k obs值与芳基
炔烃浓度的关系图呈线性,y轴上为正截距轴。该反应通过两个平行的途径进行,一个在络合物1中为第一级,在芳基
炔烃中为第一级,总体为第二级,而在一个