The first example of a mononuclear diphosphanidoargentate, bis{bis(trifluoromethyl)phosphanido}argentate, [Ag{P(CF3)(2)}(2)](-), is obtained via the reaction of HP(CF3)(2) with [Ag(CN)(2)](-) and isolated as its [K(18-crown-6)] salt. When the cyclic phosphane (PCF3)(4) is reacted with a slight excess of [K(18-crown-6)][Ag{P(CF3)(2)}(2)], selective insertion of one PCF3 unit into each silver phosphorus bond is observed, which on the basis of NMR spectroscopic evidence suggests the [Ag{P(CF3)P(CF3)(2)}(2)](-) ion. On treatment of the phosphane complexes [M(CO)(5)PH(CF3)(2)] (M = Cr, W) with [K(18-crown-6)][Ag(CN)(2)], the analogous trinuclear argentates, [Ag{(mu-P(CF3)(2))M(CO)(5)}(2)](-), are formed. The chromium compound [K(18-crown-6)][Ag{(mu-P(CF3)(2))Cr(CO)(5)}(2)] crystallizes in a noncentrosymmetric space group Fdd2 (No. 43), a = 2970.2(6) pm, b = 1584.5(3) pm, c = 1787.0(4), V = 8.410(3) nm(3), Z = 8. The C-2 symmetric anion, [Ag{(mu-P(CF3)(2))Cr(CO)(5)}(2)](-), shows a nearly linear arrangement of the P-Ag-P unit. Although the bis(pentafluorophenyl)phosphanido compound [Ag{P(C6F5)(2)}(2)](-) has not been obtained so far, the synthesis of its trinuclear counterpart, [K(18-crown-6)][Ag{(mu-P(C6F5)(2))W(CO)(5)}(2)], was successful.