The electronically unsaturated compounds Re2(CO)8[μ-Au(NHC)](μ-Ph), 1, and Re2(CO)8[μ-Au(NHC)]2, 2, were obtained from the reaction of Re2(CO)8[μ-η2-C(H)═C(H)Bun](μ-H) with MeAu(NHC), NHC = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene. Compound 1 was converted to the new compound Re2(CO)8[μ-Au(NHC)](μ-H), 3, by reaction with H2. Addition of CO to 3 yielded the new compound Re2(CO)9[Au(NHC)](μ-H), 4, which contains a terminally coordinated Au(NHC) group on one of the rhenium atoms, and the hydrido ligand was shifted to bridge the Re-Au bond. The mechanism of the formation of 4 was established by DFT computational analyses. Compound 3 also reacted with C2H2 by an addition with insertion into the Re-H bonds to yield the compound Re2(CO)8[μ-Au(NHC)](μ-C2H3), 5, which contains a σ-π coordinated, bridging C2H3 ligand. The stereochemistry of the insertion was found to proceed preferentially with a cis- (syn-) stereochemistry. Compound 1 reacted with HCl to yield Re2(CO)8[μ-Ph](μ-H), 6, and ClAu(NHC) by selective removal of the bridging Au(NHC) group. All new compounds were characterized by single-crystal X-ray diffraction analyses.