Extended covalently bonded

Depending on their coordination in the backbone network, group IV elements can form extended, covalently bonded structures of different dimensionality. As the most commonly known example, the fourfold coordination of the sp hybridized atoms leads to the three-dimensional (3D) crystalline solids diamond, c-Si, c-Ge, and a-Sn with their well-known semiconducting properties. On the other hand, linear (ID) polymer chains (XR2) with X = C, Si, Ge, Sn are based on a twofold coordination of the backbone atoms and are of great importance in organic and inorganic polymer chemistry. ... 

The reservation most commonly expressed concerning the Sneen mechanism has to do with the intervention of ion pairs in reactions of methyl and primary substrates. In accommodating these reservations, Sneen takes a liberal view as to how carbonium ion-like the species involved in the ion pair is, and describes it as having an extended covalent bond. ... 

Fig. 2 Ball and stick representations (Mercury 3.5) of the crystal structure of MEMKEU, the phosphate of thiamin, a vitamin of the B complex, wherein sulfur forms two chalcogen bonds dotted blue lines) thanks to the entrance of chloride and phosphate anions on the extended covalent bonds at sulfur SENGOH, 2-phenyl-l,2-2//-benzisoselenazole-3-one wherein selenium forms one directional chalcogen bond. CSD Refcodes and the Normalized contacts Nc, see onwards) are given. Color code gray, carbon sky-blue, nitrogen red, oxygen ocher, phosphorus light yellow, sulfur green, chlorine dark yellow, selenium...

If a covalent bond is broken, as in the simple case of dissociation of the hydrogen molecule into atoms, then theRHFwave function without the Configuration Interaction option (see Extending the Wave Function Calculation on page 37) is inappropriate. This is because the doubly occupied RHFmolecular orbital includes spurious terms that place both electrons on the same hydrogen atom, even when they are separated by an infinite distance. 

These early results have since been confirmed and extended by a vast and still growing body of research. All of the contemporary spectroscopic techniques (ir, uv, visible, nmr, esr) have been brought to bear on the problem, and further confirmation has come from cryoscopic and conductometric studies. The early confusion that resulted from the coexistence of both donor-acceptor or non-covalently-bonded complexes) has been clarified. This research has been extensively reviewed10,13-15 and will not be detailed here. 

When ionic bonds form, the atoms of one element lose electrons and the atoms of the second element gain them until both types of atoms have reached a noble-gas configuration. The same idea can be extended to covalent bonds. However, when a covalent bond forms, atoms share electrons until they reach a noble-gas configuration. Lewis called this principle the octet rule ... 

We can extend the Lewis symbols introduced in Section 2.2 to describe covalent bonding by using a line (—) to represent a shared pair of electrons. For example, the hydrogen molecule formed when two H- atoms share an electron pair (H=H) is represented by the symbol H—H. A fluorine atom has seven valence electrons and needs one more to complete its octet. It can achieve an octet by accepting a share in an electron supplied by another atom, such as another fluorine atom ... 

ABSTRACT The statistical treatment of resonating covalent bonds in metals, previously applied to hypoelectronic metals, is extended to hyperelectronic metals and to metals with two kinds of bonds. The theory leads to half-integral values of the valence for hyperelectronic metallic elements. 

A theory of resonating covalent bonds in metals, developed over the period 1938-1953 (1-3), was recently refined by the formulation of a statistical treatment for hypoelectronic metals (4). We have now extended the statistical treatment to include hyperelectronic metals. This extension has resulted not only in the evaluation of the number of resonance structures for these metals but also in the determination for them of the values of the metallic valence, which have been somewhat uncertain. 

The theory just presented shows how the behavior of electrons leads to bonding in the ground state of a molecule. When dislocations move to produce plastic deformation and hardness indentations, they disrupt such bonds in covalently bonded crystals. Thus bonds become anti-bonds (excited states). This requires that the idea of a hierarchy of states that is observed for atoms be extended to molecules. 

If electron-pair, or covalent, bonding is periodic in two or three dimensions, crystals result. The most important case is the carbon-carbon bond. If it is extended periodically in two-dimensions the result is graphite in three-dimensions it is diamond. Other elements that form electron-pair bonds are Si, Ge, and a-Sn. Some binary compounds are A1P (isoelectronic with Si),... 

The analogy between the trivalent boron compounds and car-bonium ions extends to the geometry. Although our arguments for a preferred planar structure in carbonium ions are indirect, there is electron diffraction evidence for the planar structure of boron trimethyl and the boron trihalides.298 Like carbonium ions, the boron and aluminum analogs readily form a fourth covalent bond to atoms having the requisite non-bonding electrons. Examples are the compounds with ammonia, ether, and fluoride ion.297... 

In summary, the Lewis-like model seems to predict the composition, qualitative molecular shape, and general forms of hybrids and bond functions accurately for a wide variety of main-group derivatives of transition metals. The sd-hybridization and duodectet-rule concepts for d-block elements therefore appear to offer an extended zeroth-order Lewis-like model of covalent bonding that spans main-group and transition-metal chemistry in a satisfactorily unified manner. 

---