Metal Cyanide Ions M x (CN) y ]+,- in the Gas Phase:  M = Fe, Co, Ni, Zn, Cd, Hg, Fe + Ag, Co + Ag

• Published in: Inorganic chemistry 2002-07, Vol.41 (13), p.3560-3569
• Main Authors: Dance, Ian G, Dean, Philip A. W, Fisher, Keith J, Harris, Hugh H
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic011227d

The generation of metal cyanide ions in the gas phase by laser ablation of M(CN)2 (M = Co, Ni, Zn, Cd, Hg), FeIII[FeIII(CN)6]·xH2O, Ag3[M(CN)6] (M = Fe, Co), and Ag2[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)2 n +1]- (1 ≤ n ≤ 27) and [Cd n (CN)2 n +1]- (n = 1, 2, 8−27, and possibly 29, 30). Cations Hg(CN)+ and [Hg2(CN) x ]+ (x = 1−3), and anions [Hg(CN) x ]- (x = 2, 3), are produced from Hg(CN)2. Irradiation of FeIII[FeIII(CN)6]·xH2O gives the anions [Fe(CN)2]-, [Fe(CN)3]-, [Fe2(CN)3]-, [Fe2(CN)4]-, and [Fe2(CN)5]-. When Ag3[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 Ag2[Fe(CN)5(NO)]. Homoleptic anions [Co n (CN) n +1]- (n = 1−3), [Co n (CN) n +2]- (n = 1−3), [Co2(CN)4]-, and [Co3(CN)5]- are formed when anhydrous Co(CN)2 is the target. Ablation of Ag3[Co(CN)6] yields cations [Ag n (CN) n - 1]+ (n = 1−4) and [Ag n Co(CN) n ]+ (n = 1, 2) and anions [Ag n (CN) n +1]- (n = 1−3), [Co n (CN) n - 1]- (n = 1, 2), [Ag n Co(CN) n +2]- (n = 1, 2), and [Ag n Co(CN) n +3]- (n = 0−2). The Ni(I) species [Ni n (CN) n - 1]+ (n = 1−4) and [Ni n (CN) n +1]- (n = 1−3) are produced when anhydrous Ni(CN)2 is irradiated. In all cases, CN- and polyatomic carbon nitride ions C x N y - 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 d10 metals but distorted trigonal stereochemistry for transition metals, the occurrence of M−CN−M and M(−CN−)2M 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.