Enantiopure 2-(chlorocarbonyl)phosphametallocenes [MCp*(2-COCl}-3,4-Me2-5-Ph-PC4)] (M = Fe, Ru) react with phospholide anions to give 2-phosphametallocene-2′-acylphospholides K[MCp*(2-CO-2′-3′,4′-Me2-5′-PhPC4}-3,4-Me2-5-Ph-PC4)] (M = Fe, Ru) and these have been converted into keto-bis-(2-phosphametallocene)s through reaction with [FeClCp*(tmeda)]; templation of this process with CuBr gives rise to the C2- (or pseudo-C2- when M = Ru) symmetric form of [MCp*(3,4-Me2-5-Ph-PC4)}2-2,2′-(CO)] (M = Fe, Ru; Fe, Fe) with high (>95%) diastereoselectivity. X-Ray structures of these ligands coordinated to [RuCp*Cl] and [PtCl2] centres show that the spatial orientation of the very flexible keto-bis-(2-phosphametallocene) structure is highly responsive to the coordination sphere of the chelated platinum or ruthenium centre.
不纯的 2-(
氯羰基)
磷茂
金属 [MCp*(2-COCl}-3,4-Me2-5-Ph-PC4)] (M = Fe, Ru) 与
磷酰阴离子反应生成 2-
磷茂
金属-2′-酰基
磷酰 K[MCp*(2-CO-2′-3′、4′-Me2-5′-PhPC4}-3,4-Me2-5-Ph-PC4)](M = Fe、Ru),并通过与[FeClCp*(tmeda)]反应将其转化为酮双-(2-
磷杂茂金属);用 CuBr 对这一过程进行模板化,可以得到 C2-(或 M = Ru 时的假 C2-)对称形式的 [MCp*(3,4-Me2-5-Ph-PC4)}2-2,2′-(CO)](M = Fe, Ru; Fe, Fe),非对映选择性很高(>95%)。这些
配体与[RuCp*Cl]和[PtCl2]中心配位的 X 射线结构表明,非常灵活的酮双-(2-
磷杂茂金属)结构的空间取向对螯合
铂或
钌中心的配位圈具有很高的响应性。