Study on iron–sulfur cluster in gas phase: electronic structure and reactivity

Evolution of the structure and electronic properties of neutral and anion (n=1–7, μ=0, −1) clusters: A comprehensive analysis

“…It worth pointing out that our calculated results agree well with that obtained by Zhai et al [13] and Nakajima et al [14]. All calculations were performed with the GAUSSIAN03 program [53].…”

“…For example, according to the photoelectron spectroscopic (PES) experiment of FeS À n (n = 1-6) clusters, Zhai et al proposed that the Fe atom is likely to maintain its favorite + 3 oxidation state in all the FeS À n (n > 1) clusters with (S 2À m )Fe 3+ (S 2À nÀm ) type of structures [13]. The electronic structure and reactivity of Fe n S À m (n = 1-8, m = 2-6) clusters were first investigated by Nakajima et al [14] using PES with different photon energies. The results show that their electronic affinities (EAs) greatly change at the composition of n = m where the clusters are more stable.…”

The electronic states of Fe2S2−/0/+/2+

“…Fe n S m ϩ clusters have been generated also by reaction of Fe n ϩ with CS 2 , 4 and neutral Fe n S m clusters have been observed as a reaction product of Fe n and H 2 S. 5 Electron affinities have been obtained from photoelectron spectra of cluster anions. 6,7 A selective way for the gas phase synthesis of Fe 2 S 2 ϩ has been described. 8 Differently charged FeS species have been studied in detail.…”

The challenge of generating iron-sulfur clusters

“…Toward this goal we intend to pursue a completely new approach by mimicking the catalytically active centers of iron-sulfur proteins in the form of gas phase clusters and by studying their intrinsic redox activity and catalytic properties. Since both theoretical and experimental studies on the structure [3][4][5][6][7] and reactivity [8][9][10][11][12][13][14] of free iron-sulfur clusters are still scarce and have only been reported for selected systems, comprehensive investigations of the influence of cluster size, composition and charge on the cluster properties are of particular interest. This will allow to gain insight into fundamental processes on a strictly molecular level and to develop general concepts.…”

“…In the literature three different methods for the generation of free iron-sulfur clusters are described: (1) the generation of iron clusters and subsequent reaction of those with C 2 H 4 S, COS, or CS 2 [12,15], (2) the generation of ligated iron-sulfur anions via electrospray ionization [5], and (3) the laser ablation of binary iron-sulfur targets [9,10,14,[16][17][18][19]. These latter targets are typically fabricated by compressing a mixture of iron and sulfur powder of different compositions.…”