In THF solution the dirhenium complex Re-2(mu-H)(mu-PCy(2))(CO)(8) (1) reacts with an equimolar amount of LiPh at -100 degrees C to afford after warming up to room temperature within 1 h the salt Li[Re-2(mu-H)(mu-PCy(2))(C(Ph)O)(CO)(7)] (Li[2]). Through cation exchange of Li+ against PPh(4)(+), Li[2] gives the airstable solid PPh(4)[2] in 86% yield. The selectivity of the LiPh attack atone of the four axial carbonyls in 1 was proved by the chiral shift reagent Eu(hfac)(3) which was dissolved in a CDCl3 solution of PPh(4)[2]. The H-1 and P-31 NMR spectra show the diastereomeric resolution of the respective peaks in an integral ratio of 1:1 e.g. Delta delta(mu-P) 0.43. The anion [2(-)] generates with 2 equiv of XAuPPh(3) (X=Cl, Br, I) in THF at room temperature within 15 min under release of the leaving group PhCHO the yellow cluster complexes Re-2(AuPPh(3))(2)(mu-PCy(2))(CO)(7)X (3a-c). Their precursor complex anions [Re-2(mu-AuPPh(3))(mu-PCy(2))(CO)(7)X](-) (3a-c) are obtained from 1 and an equimolar amount of XAuPPh(3) or from the deauration by treatment of 4a (X=Cl) with 1 equiv of LiPh via a transmetalation reaction. Such anions are isolable as salts, N(PPh(3))(2)[3a-c]. All new cluster complexes are identified by means of H-1 NMR, P-31 NMR and nu(CO) IR spectroscopic measurements, Li[2] and 4a (X=Cl) additionally by means of X-ray single-crystal structure analyses. Li[2] crystallizes triclinic, space group , Z=2, a=10.536(2) Angstrom, b=11.433(2) Angstrom, c=19.125(3) Angstrom, alpha=98.01(1)degrees, beta=89.94(1)degrees, and gamma=112.22(1)degrees; 4a crystallizes monoclinic, space group P2(1)/c, with Z=4, a=18.615(5) Angstrom, b=13.606(2) Angstrom, c=24.223(6) Angstrom, and beta=105.14(2)degrees. The molecular structure of Li[2] shows a mu-H-, mu-P-bridged Re-Re bond of 3.1667(7) Angstrom, the one of 4a a tetrahedrally shaped Re2Au2 core with a mu-P-bridged Re-Re edge of 3.2680(10) Angstrom.