The generation of metal cyanide ions in the gas phase by laser ablation of M(CN)(2) V = Co, Ni, Zn, Cd, Hg), Fe-III[Fe-III(CN)(6)].xH(2)O, Ag-3[M(CN)e] (M = Fe, Co), and Ag-2[Fe(CN)(5)(NO)] has been investigated using Fourier transform ion cyclotron resonance mass spectrometry. Irradiation of Zn(CN)2 and Cd(CN)2 produced extensive series of anions, [Zn-n(CN)(2n+1)](-) (1 less than or equal to n less than or equal to 27) and [Cd-n(CN)(2n+1)](-) (n = 1, 2, 8-27, and possibly 29, 30). Cations Hg(CN)l and [Hg-2(CN)(x)](+) (x = 1-3), and anions [Hg(CN),]- (x = 2, 3), are produced from Hg(CN)(2). Irradiation of Fe-III [Fe-III(CN)(6)] . xH(2)O gives the anions [Fe(CN)(2)](-), [Fe(CN)(3)](-), [Fe-2(CN)(3)](-), [Fe-2(CN)(4)](-), and [Fe-2(CN)(5)]-. When Ag-3[Fe(CN)(6)] is ablated, [AgFe(CN)(4)](-) and [Ag2Fe(CN)(5)](-) are observed together with homoleptic anions of Fe and Ag, The additional heterometallic complexes [AgFe2(CN)(6)](-), [AgFe3(CN)(8)](-), [Ag2Fe2(CN)(7)](-), and [Ag3Fe(CN)(6)] are observed on ablation of Ag-2[Fe(CN)(5)(NO)]. Homoleptic anions [Co-n(CN)(n+1)](-) (n = 1-3), [Co-n(CN)(n+2])(-) (n = 1-3), [Co-2(CN)(4)](-), and [Co-3(CN)(5)](-) are formed when anhydrous Co(CN)(2) is the target. Ablation of Ag-3[CO(CN)(6)] yields cations [Ag-n(CN)(n-1)](+) (n = 1-4) and [AgnCo(CN)(n)](+) (n = 1, 2) and anions [Ag,(CN),,]- (n = 1-3), [Co,(CN),-,](n = 1, 2), [AgnCo(CN)(n+2)](-) (n = 1, 2), and [AgnCo(CN)(n+3)](-) (n = 0-2). The Ni(l) species [Ni-n(CN)(n-1) (n = 1-4) and [Ni,(CN),,]-(n = 1-3) are produced when anhydrous Ni(CN)2 is irradiated. In all cases, CN- and polyatomic carbon nitride ions CxNy- are formed concurrently. On the basis of density functional calculations, probable structures are proposed for most of the newly observed species. General structural features are low coordination numbers, regular trigonal coordination stereochemistry for d(10) metals but distorted trigonal stereochemistry for transition metals, the occurrence of M-CN-M and M(-CN-)(2)M bridges, addition of AgCN to terminal CN ligands, and the occurrence of high spin ground states for linear [M-n(CN)(n+1)]- complexes of Co and Ni.