Formation of a rhenium(III) carbonyl complex by electrophilic attack on rhenium isocyanides. Synthesis and molecular structure of {Re[N(CH 2CH 2S) 3][CNC(CH 3) 3]} and {Re[N(CH 2CH 2) 3](CO)}

Abstract

Treatment of the trigonal-bipyramidal complex {Re[N(CH 2CH 2S) 3](CNCH 2COOEt)} ( 1a) with LiOH in THF leads to ester hydrolysis and yields the complex {Re[N(CH 2CH 2S) 3](CNCH 2COOH)} ( 2). Attempts to hydrolyze the ester in 1a in the two-phase system toluene/concentrated hydrochloric acid proceeded under electrophilic attack at the isocyanide nitrogen atom and formation of the carbonyl complex {Re[N(CH 2CH 2S) 3](CO)} ( 3). Complex 3 was also obtained by treatment of {Re[N(CH 2CH 2S) 3][CNC(CH 3) 3]} ( 1b) with toluene/hydrochloric acid. The molecular structures of 1b and 3 were established by X-ray structure analysis.