A lithium-halogen exchange route has been developed to generate acyclic diaminocarbenes (ADC) from chloroamidinium salts. Convenient access to various ADC complexes (B, Rh, Ir, Pd) stems from a one-pot transmetalation protocol. Formation of a carbenoid species is suggested by 1D and 2D NMR studies with a (13)C-labeled chloroamidinium precursor and also by X-ray structures of transition metal-carbene complexes. Rh-ADC complex 4 is an effective catalyst for the 1,2-addition of aryl boronic acids to aryl aldehydes.