Addition of RLi (R = Ph, Me) to [Ru 6 C(CO) 1 4 (η 6 -C 6 H 6 )] (1) or [Ru 6 C(CO) 1 2 (η 6 -C 6 H 6 ) (μ 2 -η 2 :η 2 -C 6 H 8 )] (2), followed by reaction with [AuPPh 3 Cl]/T1PF 6 , leads to the formation of the mixed ruthenium-gold cluster complexes [Ru 6 C(CO) 1 4 (η 4 -C 6 H 6 R 2 )(AuPPh 3 ) 2 ] (5a, b) and [Ru 6 C(CO) 1 2 (η 6 -C 6 H 5 R) (μ 2 -η 2 :η 2 -C 6 H 8 )(AuPPh 3 )] (6a, b), respectively. Treatment of the likely intermediate products, the cluster salts (PPN) 2 [Ru 6 C(CO) 1 4 (η 4 -C 6 H 6 R 2 )] (3a, b) and (PPN) 2 [Ru 6 C(CO) 1 2 (η 5 -C 6 H 6 R) (μ 2 -η 2 :η 2 -C 6 H 8 )] (4a, b) (PPN = [N(PPh 3 ) 2 ] + ) with [CPh 3 ][BF 4 ] affords hydride abstraction and gives the substituted arene cluster complexes [Ru 6 C(CO) 1 4 (η 6 -C 6 H 4 R 2 )] (7a, b) and [Ru 6 C(CO) 1 2 (η 6 -C 6 H 5 R) (μ 2 -η 2 :η 2 -C 6 H 8 )] (8a, b), respectively. The crystal and molecular structures of [Ru 6 C(CO) 1 4 (η 6 -C 6 H 4 Ph 2 )] (7a) and of two polymorphs of [Ru 6 C(CO) 1 4 (η 6 -C 6 H 4 Me 2 )] (7b) are established by X-ray crystallography. The molecules have a p-terphenyl (7a) and a p-xylene (7b) ligand η 6 -coordinated to a vertex of a Ru 6 octahedron.