Main Group Element Sulfides

Barthelmehs, K. L., G. V. Gibbs, and M. B. Boisen, Jr. (1990). Bond length and bonded radii variations in sulfide molecules and crystals containing main group elements a comparison with oxides. Amer. Mineral 74, 620-26. 

Main group element derivatives containing three or four ferrocenyl thiolate ligands are accessible from the corresponding element chlorides and Fc-SLi. Thus, the reaction of PCI3 with a suspension of 3 equivalents Fc-SLi in toluene — THF (3 1) leads to tris(ferrocenyl thiolato) phosphine, P(SFc)3 the oxide and sulfide, P(0)(SFc)3 and P(S)(SFc)3, are formed as side-products in addition to Fc-SS-Fc. The corresponding tris (ferrocenyl thiolato) element compounds As(SFc)3 and Sb(SFc)3 are also known the antimony derivative decomposes under the influence of either air or light [235]. 

In metals the valence shell is formed by the s or d band. The main-group elements with their s bands are typical electron donors and form strong bonds with electron acceptors such as sulfur or oxygen stable sulfides and oxides are formed. These metals are therefore not suitable as catalysts. In contrast the transition metals with their d bands are excellent catalysts. It is noteworthy that both hydrogenations and oxidations can be carried out with d-block elements. 

The first compound of this series, CeSI, was reported by Carter (68) in 1961, and later discussed by Dagron (93). It was obtained by the reaction of iodine with cerium sulfide at 430 C, or by direct synthesis from the elements at 500°C. This was the start of a detailed investigation of this group of compounds mainly by Dagron and co-workers. The present situation is presented in Table VII. No scandium compounds are known thus far, and the same is true for selenium and tellurium halides of these elements. 

Knowledge of the 90 chemical elements and their properties in compounds led to the construction, by man, of a unique table of elements, the Periodic Table, of 18 Groups in six periods in a pattern fully explained by quantum theory, described in Chapter 2. There is then a huge variety of chemical combinations possible on the Earth and limitations on what is observable are related to element position in this Table. It also relates to the thermodynamic and/or kinetic stability of particular combinations of them in given physical circumstances (Table 11.3). The initial state of the surface of the Earth with which we are concerned was a dynamic water layer, the sea, covering a crust mainly of oxides and some sulfides and with an atmosphere of NH3, HCN, N2, C02(C0, CH4), H20, with some H2 but no 02. This combination of phases and their contents then produced an aqueous solution layer of particular components in which there were many concentration restrictions between it and the components of the other two layers due to thermodynamic stability, equilibria, or kinetic stability of the chemicals trapped in the phases. It is the case that equilibrium... 

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