The reaction of AgClO4 with piperidinium 2,7-di-tert-butyl-9H-fluorene-9-carbodithioate (pipH)[S2C(t-Bu-Hfy)] (1) (t-Bu-Hfy = 2,7-di-tert-butylfluoren-9-yl) afforded [Ag-n{S2C(t-Bu-Hfy)}(n)] (2), which reacted with phosphines to give [Ag{S2C(t-Bu-Hfy)}L-2] [L = PPh3 (3a); L-2 = bis(diphenylphosphino)ethane (dppe, 3b), 1,1'-bis(diphenylphosphino)ferrocene (dppf, 3c). By reacting complex 2 with AgClO4 and piperidine in a 1:1:1 molar ratio, the dodecanuclear cluster [Ag-12{S2C=(t-Bu-fy)}(6)] (4) (t-Bu-fy = 2,7-di-tert-butylfluoren-9-ylidene) was obtained. Compound 4 can also be directly prepared from the reaction of 1 with AgClO4 and piperidine in a 1:2:1 molar ratio. The reactions of 1 with AgClO4, phosphines, and piperidine afforded the compounds [Ag-6{S2C=(t-Bu-fy)}(3)L-5] [1:2:2:1 molar ratio; L = PPh3 (5a), P(p-To)(3) (5b)], [Ag-4{S2C=(t-Bu-fy)}(2)(dppf)(2)] (6) (1:2:1:1 molar ratio), [Ag-n{S2C=(t-Bu-fy)}(n/2){P(i-Pr)(3)}(n)] (7) (1:2:2:1 molar ratio), or [Ag-8{S2C=(t-Bu-fy)}(4){P(i-Pr)(3)}(4)] (8) (1:2:1:1 molar ratio). Complexes 5a,b, 6, 7, and 8 can be also obtained by reacting 4 with the corresponding phosphine in the appropriate molar ratio. The crystal structures of 4, 5b, and 8 have been determined by X-ray diffraction studies. The nuclearity of complex 6 was established from its P-31{H-1} NMR data, which reveal a very fast dynamic process leading to an average coupling of each of the P atoms of the dppf ligands with four Ag atoms.