Treatment of [NEt4](3)[HRe6C(CO)(18)] in acetone with Au(PPh3)Cl (1 equiv) provides the gold-capped cluster [NEt4](2)-[HRe6C(CO)(18)(AuPPh3)] (1) (82%). Compound 1 crystallizes in the monoclinic space group P2(1)/c with a=16.519(4) Angstrom, b=17.849(5) Angstrom, c=21.540(5) Angstrom, beta=99.870(7)degrees, and Z=4. The X-ray structure solution shows the cluster anion consists of an octahedral core of rhenium atoms centered on an interstitial carbide with one face capped by a triphenylphosphinegold moiety. Carbonyl ligand positions imply that the hydride ligand is bridging an edge of the Res face trans to the gold cap. Support for this structure is provided by the solution C-13 NMR spectrum of 1 recorded at low temperature. The reaction of Au(PPh3)Cl (2 equiv) with either [NEt4](3)[HRe6C(CO)(18)] or [NEt4](2)[H2Re6C(CO)(18)] in acetone in the presence of the strong base DBU provides the digold cluster [NEt4](2)-[Re6C(CO)(18)(AuPPh3)(2)] (2) (85%). The X-ray crystal structure of 2 as an acetone solvate (monoclinic, P2(1)/a, a =19.956(4) Angstrom, b=21.822(5) Angstrom, c=18.578(5) Angstrom, beta=98.99(1)degrees, Z=4) shows a Re-6(mu(6)-C) octahedral core with trans (1,4) faces capped by the triphenylphosphinegold moieties. Treatment of [NEt4](3)[HRe6C(CO)(18)] in acetone with the more electrophilic reagent AuPPh3(NO3) yields [NEt4][HRe6C(CO)(18)(AuPPh3)(2)] (3) (52%). The low-temperature C-13 NMR spectrum of 3 suggests a 1,4-dicapped structure with a hydride ligand bridging an edge linking the two gold-capped faces. Compound 3 is slowly deprotonated by triethylamine to give 2.