Group 14 elements silicon

S. Nagase, Polyhedral compounds of the heavier group 14 elements silicon, germanium, tin and lead. Acc. Chem. Res. 28, 469-76 (1995). 

Currently, there is growing interest in polymers the frameworks of which are constructed from the Group 14 elements silicon, germanium and tin. Several reviews on polysilanes have appeared in the literature . In the first section of this article we focus on recent developments in the chemistry of polygermanes and polystannanes. The chemistry and structure-property relationship of oligostannanes and low molecular weight polystannanes was the subject of earlier reviews . ... 

Among the salts of Group 14 elements, silicon compounds are especially sensitive to moisture and they easily react with water and ethanol at room temperature to give the corresponding dithiocarboxylic acids [7,12,13]. In contrast. 

Metallocanes of group 14 elements - silicon and germanium derivatives 06KGS1777. 

One of the group 14 elements silicon, placed just below C in the conventional periodic table, plays an important role in the lithosphere of the Earth s crust, just as carbon does in the biosphere. The composition of the Earth s cmst may... 

The main-group elements are sometimes called the representative elements because they have a wide range of properties. At room temperature and atmospheric pressure, many are solids, while others are liquids or gases. About half of the main-group elements are metals. Many are extremely reactive, while several are nonreactive. The main-group elements silicon and oxygen account for four of every five atoms found on or near Earth s surface. 

Silicon (3), which resembles metals in its chemical behavior, generally has a valence of +4. In a few compounds it exhibits a +2 valence, and in silicides it exists as a negative ion and largely violates the normal valency rules. Silicon, carbon, germanium, tin, and lead comprise the Group 14 (IVA) elements. Silicon and carbon form the carbide, SiC (see Carbides). Silicon and germanium are isomorphous and thus mutually soluble in all proportions. Neither tin nor lead reacts with silicon. Molten silicon is immiscible in both molten tin and molten lead. 

This fundamental discovery dramatically affected the whole chemistry of main-group elements. Subsequently, a series of new compounds with silicon element multiple bonds has been introduced. Within only a few years, stable silenes (silaethenes with a Si = C double bond) [8-11], silaimines Si = N [12-14], and silaphosphenes Si = P [15] were synthesized. As a pacemaker, silicon chemistry has exerted a strong influence on further areas of main-group chemistry a variety of stable molecules with Ge = Ge [16], P = P [17], As = As [18], P = C and P = C [19-22] bonds were subsequently isolated, and systems with cumulated double bonds P = C = P [23-25] are also known today. 

Other heterocyclosiloxanes in which one or more of the skeletal silicon atoms have been replaced by an atom of another main group element or transition metal are well-known and have been extensively studied [136],... 

Compounds of multiple bond systems involving heavier main group elements were long considered to be unstable and synthetically inaccessible. In particular, the so-called double bond rule, which forbade the formation of (pn-pn) multiple bonds between silicon and other elements, hindered the development of the chemistry of low-coordinate silicon compounds containing Si=X (X = C, N, Si, P) double bonds for some years. 

In recent years considerable research has been done on the photochemistry and thermal chemistry of main group element azides,37 especially those of silicon. Monoazidosilanes have long been employed in the photochemical generation of iminosilanes.38,39 These products arise from the thermal or photochemical loss of molecular nitrogen accompanied by a 1,2-shift of a substituent from silicon to nitrogen. 

Silicon-containing ceramics include the oxide materials, silica and the silicates the binary compounds of silicon with non-metals, principally silicon carbide and silicon nitride silicon oxynitride and the sialons main group and transition metal silicides, and, finally, elemental silicon itself. There is a vigorous research activity throughout the world on the preparation of all of these classes of solid silicon compounds by the newer preparative techniques. In this report, we will focus on silicon carbide and silicon nitride. 

Tetravalent silicon is the only structural feature in all silicon sources in nature, e.g. the silicates and silica even elemental silicon exhibits tetravalency. Tetravalent silicon is considered to be an ana-logon to its group 14 homologue carbon and in fact there are a lot of similarities in the chemistry of both elements. Furthermore, silicon is tetravalent in all industrially used compounds, e.g. silanes, polymers, ceramics, and fumed silica. Also the reactions of subvalent and / or low coordinated silicon compounds normally lead back to tetravalent silicon species. It is therefore not surprising that more than 90% of the relevant literature deals with tetravalent silicon. The following examples illustrate why "ordinary" tetravalent silicon is still an attractive field for research activities Simple and small tetravalent silicon compounds - sometimes very difficult to synthesize - are used by theoreticians and preparative chemists as model compounds for a deeper insight into structural features and the study of the reactivity influenced by different substituents on the silicon center. As an example for industrial applications, the chemical vapor decomposition (CVD) of appropriate silicon precursors to produce thin ceramic coatings on various substrates may be mentioned. 

The chemistry of carbon, known as organic chemistry, has i already been discussed. The element silicon, also in Group IV, is just as significant in the mineral world as carbon is in the world of living things. Silicon is the second most abundant element in the earth s crust (oxygen is the most abundant). 

The ability to insert in many element-element bonds is an important property of 1 the r -p1 rearrangement of the pentamethylcyclopentadienyl ligands during the reaction is a prerequisite to show a silylene-type reactivity. From a preparative point of view it is worth mentioning that element-silicon bonds which otherwise are difficult to form are easily accessible with the help of 1. In addition, the leaving group character of the pentamethylcyclopentadienyl substituents allows further chemical transformations (vide infra). 

The noticeable renaissance of main group chemistry is well reflected by the relatively large number of structures with main group elements determined by electron diffraction. Consider as examples the molecules with boron, silicon, phosphorus, or sulfur. 

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