Catalytic Allylic Alkylation and Allylic Phenolation Reactions with Ruthenium Complexes. Solid-State Structures of a Model Catalytic DMF Intermediate, [Ru(Cp*)(Cl)(η³-C₃H₅)(DMF)](PF₆), and a New Tetranuclear Salt, [Ru(Cp){Ru(Cp)(η⁶-<i>p</i>-CH₃C₆H₄CN)}₃](PF₆)₄

Abstract

Results from Ru-catalyzed (i) allylic alkylation reactions for linear and branched para-substituted aryl carbonates, p-R1C6H4CHCHCH2OCO2But and p-R1C6H4CH(OCO2But)-CHCH2, with dimethyl malonate and (ii) allylic phenolation reactions using C6H5CH(OCO2But)CHCH2 and phenol compounds are presented. The possible role of the π-arene complexes [Ru(Cp*)(η6-p-XC6H4CHCHCH2OCO2But)]PF6 is discussed. Solid-state structures for [Ru(Cp*)(Cl)(η3-C3H5)(DMF)](PF6) (12) and a new tetranuclear salt, [Ru(Cp){Ru(Cp)(η6-p-CH3C6H4CN)}3](PF6)4, based on toluinitrile, are presented. Analysis of the solid-state data for the model salt 12 provides a partial understanding with respect to how several factors, e.g., the choice of solvent and the nature of the reagents themselves, might affect the regioselectivity of these reactions