The [(η⁵-C₅Me₅)(2,2‘-bipyridine)Ru]^- Anion and Its Use in the Synthesis of Alkyl, Gallyl, and Stannyl Complexes of Ruthenium

Abstract

Reduction of Cp*(bipy)RuCl (Cp* = η 5 -C 5 Me 5, bipy = 2,2‘-bipyridine) with an excess of KC 8 in THF generated the dark purple-red anionic ruthenium complex K[Cp*Ru(bipy)] ( 2a ). The analogous lithium salt Li[Cp*Ru(bipy)] ( 2b ) was generated in situ by reaction of Cp*(bipy)RuCl with 2 equiv of lithium naphthalenide. Complex 2a was structurally characterized as the crown adduct [K(dibenzo-18-crown-6)][Cp*Ru(bipy)] ( 2a· dibenzo-18-crown-6). Dark purple crystals of this complex were obtained from a THF/pentane solution, and its structure was determined by X-ray diffraction. The solid state structure features two ion pairs of 2a in its asymmetric unit. In a reaction with MeI, compound 2a was converted to the methyl complex Cp*(bipy)RuMe ( 3 ). Complex 2a reacted with Me 3 SnCl to produce the ruthenium stannyl complex Cp*(bipy)RuSnMe 3 ( 4 ). Reaction of 2a with TripGaCl 2 (THF) in THF gave the ruthenium gallyl derivative Cp*(bipy)Ru(GaClTrip) ( 5 ).