Development of complexes with a Multiple Bond between Transition Metal and Phosphor us

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The reaction of [Cp(CO)ィイD22ィエD2(SnィイD1nィエD1BuィイD23ィエD2)W{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe(OMe)}] with a Lewis acid revealed the formation of a phosphenium complex, followed by migration of a ィイD1nィエD1BU group from Sn to P to give a stannylene complex. If the reaction takes place in the presence of NaBPhィイD24ィエD2, a phosphi de complex, Cp(CO)ィイD22ィエD2W{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe} is formed. This unprecedented reaction is considered to be a W-P bond order increment by one with elimination of a stannyl and a methoxy group. The reaction proceeds with one electron reducti on of a phosphenium complex by NaBPh4, followed by stannyl radical elimination.The reaction of a Lewis acid with a ruthenium complex, [Cp(CO)(ERィイD23ィエD2)Ru-{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe(OMe)}] (where E = C, Si , Ge, Sn), which has both diamino-substituted phosphite and a group 14 element ligand was examined. Irrespective of the kind of E, an OMe group on the phosphorus is abstracted as an anion to give a phosphenium complex. The following reaction depends on the kind of E. If ERィイD23ィエD2 is an alkyl group, the ligand migrates from Ru to the phospheni um phosphorus, whereas if ERィイD23ィエD2 is a silyl or a germyl group, no migration reaction takes place. If ERィイD23ィエD2 is a stannyl group, an al kyl group on the tin migrates to the phosphenium phosphorus to give a stannylene complex, which has a double bond between Ru and Sn.The reaction of a Lewis acid with [Cp(CO)(SiMeィイD22ィエD2OMe)Fe{PN(Me)CHィイD22ィエD2CHィイD22ィエD2-NMe(OMe)}] containing an OR group on both coordinating P and Si atoms revealed that selective OR abstraction from Si occurs to give a silylene complex.