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Concept
Silicon–oxygen bond
Résumé
A silicon–oxygen bond ( bond) is a chemical bond between silicon and oxygen atoms that can be found in many inorganic and organic compounds. In a silicon–oxygen bond, electrons are shared unequally between the two atoms, with oxygen taking the larger share due to its greater electronegativity. This polarisation means Si–O bonds show characteristics of both covalent and ionic bonds. Compounds containing silicon–oxygen bonds include materials of major geological and industrial significance such as silica, silicate minerals and silicone polymers like polydimethylsiloxane.
On the Pauling electronegativity scale, silicon has an electronegativity of 1.90 and oxygen 3.44. The electronegativity difference between the elements is therefore 1.54. Because of this moderately large difference in electronegativities, the bond is polar but not fully ionic. Carbon has an electronegativity of 2.55 so carbon–oxygen bonds have an electronegativity difference of 0.89 and are less polar than silicon–oxygen bonds. Silicon–oxygen bonds are therefore covalent and polar, with a partial positive charge on silicon and a partial negative charge on oxygen: Siδ+—Oδ−.
Silicon–oxygen single bonds are longer (1.6 vs 1.4 Å) but stronger (452 vs. about 360 kJ mol−1) than carbon–oxygen single bonds. However, silicon–oxygen double bonds are weaker than carbon–oxygen double bonds (590 vs. 715 kJ mol−1) due to a better overlap of p orbitals forming a stronger pi bond in the latter. This is an example of the double bond rule. For these reasons, carbon dioxide is a molecular gas containing two C=O double bonds per carbon atom whereas silicon dioxide is a polymeric solid containing four Si–O single bonds per silicon atom; molecular SiO2 containing two Si=O double bonds would polymerise. Other compounds containing Si=O double bonds are normally very reactive and unstable with respect to polymerisation or oligomerization. Silanones oligomerise to siloxanes unless they are stabilised, for example by coordination to a metal centre, coordination to Lewis acids or bases, or by steric shielding.
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