Treatment of [RhR(CNBut)4I][BF4](R = Me or Et) with neat R′NH2 (R′= Me, Prn, or Bun) leads to the formation of the chelated dicarbene complexes [[graphic omitted](NHBut)}R(CNBut)2I][BF4]. An alternative route to the dicarbene complex where R = Me and R′= Prn is reaction of [Rh{C(NHPrn)(NHBut)}Me(CNBut)3I][BF4] with neat propylamine. Reaction of [RhMe(CNBut)4I]+ with neat hydrazine affords a related dicarbene complex analogous to the Chugaveff salts. The use of neat amine as solvent in these reactions is extended to the synthesis of related 2.2′-bipyridyl and 1.10-phenanthroline iron (II) dicarbene complexes. The nature of the bonding and the mechanism of formation of these species is discussed.