Synthesis of Fischer type-carbene complexes containing a coordinated thioimidate structural motif

This paper describes a tandem strategy to synthesize a series of new Fischer carbene complexes (CO)(4)Mdouble bond, length as m-dash]CN-(CH(2))(4)-]CHdouble bond, length as m-dash]C(NRR')(SR'); M = Cr, W; R = Ar, R' = Me, -(CH(2))(2)-] with a thioimide or thiazoline fragment, in which the sulfur or nitrogen atom is coordinated to a metal center, depending on the nature of alkylating groups included as R'. We have trapped by protonation the proposed intermediate as the thioamide 12 (CO)(5)Wdouble bond, length as m-dash]CN-(CH(2))(4)-]CH(2)C(S)NHPh], which reveals the pathway of this reaction.