Synthesis of functionalized phenyl, 2-thienyl, and N-methyl-pyrrol-2-yl Fischer carbene complexes of chromium and tungsten was achieved via a Negishi cross-coupling reaction of metalated aminocarbenes in the presence of a palladium catalyst. The reverse approach, i.e., coupling bromocarbenes with organozinc reagents, is also feasible and is particularly useful with alkoxycarbene complexes, metalation of which is not possible. Both these procedures are also suitable for the cross-coupling of molybdenum amino- and alkoxycarbene complexes. The presented methodology enables an access to the new amino and alkoxy carbene complexes bearing aldehyde, ketone, nitrile, and ester functionality.

Thiophene-and furan-derived aminocarbene complexes are regioselectively lithiated by BuLi at position 5, while lithiated aminocarbenes containing pyrrole or phenyl groups can be obtained by a bromine to lithium exchange reaction using BuLi. Such prepared lithiated aminocarbene complexes react with alkyl halides, aldehydes, ketones, acyl chlorides, and DMF, giving high yields of functionalized aminocarbene complexes hardly accessible by other ways.