Reaction of aminophosphinimine [RHN(CH(2))(2)N[double bond, length as m-dash]PPh(3)] (R = H, Et) with Re(2)(CO)(10) provided the NH-functionalized carbene rhenium complex [Re(2)(CNHCH(2)CH(2)NR)(CO)(9)] (3a, R = H, 3b, R = Et). Treatment of 3 with Br(2) provided the mono nuclear [Re(CNHCH(2)CH(2)NR)(CO)(4)Br] (1, R = H, 2, R = Et). However, NH-functionalized carbene complexes 1-3 did not undergo N-alkylation with alkyl halides to yield the N-substituted NHC complexes. The direct ligand substitution of [Re(CO)(5)Br] with a carbene donor was employed to prepare [Re(IMes(2))(CO)(4)Br] (6a, IMes(2) = 1,3-di-mesitylimidazol-2-ylidene; 6b, IMes(2) = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene). Analyses of spectroscopic and crystal data of 6a and 6b show similar corresponding data among these complexes, suggesting the saturated and unsaturated NHCs have similar bonding with Re(I) metal centers. Reduction of 6a and 6b with LiEt(3)BH yielded the corresponding hydrido complexes 7a-b [ReH(CO)(4)(IMes(2))], but not 1 and 2. Ligand substitution of 1, 6a and 6b toward 2,2'-bipyridine (bipy) was investigated. Crystal structures of 1, 3a-b, 6a-b and 7b were determined for characterization and comparison.