Si-O bond

Note the much larger enthalpy of formation of silieon dioxide as compared with carbon dioxide this arises in part because of greater strength in the Si—O bonds and also because the Si—Si bond in silieon is mueh weaker than the C—C bond (p. 162). 

This greater reactivity of the silanes may be due to several factors, for example, the easier approach of an oxygen molecule (which may attach initially to the silane by use of the vacant silicon d orbitals) and the formation of strong Si—O bonds (stronger than C—O). 

Witir the correct choice of the parameters k and the ah initio data in Figure 4.50 could be reproduced very well. In this force field a Urey-Bradley term was also included between the silicon atoms in such angles to model the lengthening of the Si—O bond as the angle decreased. 

At the temperature limits of thek stabiHty ranges, the main forms of siHca interconvert. The transformations involve a change in the secondary (nonnearest-neighbor) coordination and requke the breaking and reformation of Si—O bonds. The transformation processes, known as reconstmctive polymorphic transformations (44), are slow, as shown by the fact that the high temperature polymorphs can persist outside thek normal stabiHty range. 

The tetrahedral network can be considered the idealized stmcture of vitreous siUca. Disorder is present but the basic bonding scheme is still intact. An additional level of disorder occurs because the atomic arrangement can deviate from the hiUy bonded, stoichiometric form through the introduction of intrinsic (stmctural) defects and impurities. These perturbations in the stmcture have significant effects on many of the physical properties. A key concern is whether any of these defects breaks the Si—O bonds that hold the tetrahedral network together. Fracturing these links produces a less viscous stmcture which can respond more readily to thermal and mechanical changes. 

Fig. 7. Schematic description of a polysiloxane at the monolayer—substrate surface (4). The arrow points to an equatorial Si—O bond that can be connected either to another polysiloxane chain or to the surface. The dashed line on the left is a bond in a possible precursor trimer where the alkyl chains can occupy...

Bu4N F , THF, "2 min. The TBDS group is less reactive toward tri-ethylammonium fluoride than is the TIPDS group. It is stable to 2 M HCl, aq. dioxane, oyemight. Treatment with 0.2 MNaOH, aq. dioxane leads to cleavage of only the Si—O bond at the 5 -position of the uridine derivative. The TBDS derivative is 25 times more stable than the TIPDS derivative to basic hydrolysis. 

Silyl-derived protective groups are also used to mask the thiol function. A complete compilation is not given here since silyl derivatives are described in the section on alcohol protection. The formation and cleavage of silyl thioethers proceed analogously to simple alcohols. The Si—S bond is weaker than the Si—O bond, and therefore sulfur derivatives are more susceptible to hydrolysis. For the most part silyl ethers are rarely used to protect the thiol function because of their instability. Silyl ethers have been used for in situ protection of the — SH group during amide formation. ... 

Since both Si—O and Si—CHj bonds are thermally stable it is predictable that the polydimethylsiloxanes (dimethylsilicones) will have good thermal stability and this is found to be the case. On the other hand since the Si—O bond is partially ionic (51%) it is relatively easily broken by concentrated acids and alkalis at room temperature. 

The adhesion of the tobermorite particles to each other and to the embedded aggregates is responsible for the strength of the cement which is due, ultimately, to the formation of -Si-O-Si-O bonds. 

There are a variety of silicates, which can be viewed as various arrangements of tetrahedral oxoanions of silicon in which each Si—O bond has considerable covalent character. The differences in properties between the various silicates are related to the number of negative charges on each tetrahedron, the number of corner O atoms shared with other tetrahedra, and the manner in which chains and sheets of the linked tetrahedra lie together. Differences in the internal structures of... 

It can be seen that although the Si-O bond distances within the polyhedral skeleton are not unusually long (cf. an average distance of 1.629 A for four-coordinate Si attached to two coordinate the Si-O-Si angles, varying from about 114.5 to 118.5°, are much sharper than is common in unstrained systems... 

The Tg-based octa-anion TglO lg can be seen as a model for the well-known D4R found in inorganic structures such as zeolite A. Synthesis of TglO Jg can be achieved more readily than many other POSS species and it can be obtained in quantitative yield from the reaction of a tetra-alkoxysilane with H2O (10 equiv./Si) in the presence of Me4NOH (1 equiv./Si) in methanol at room temperature for 1 day (Figure Alcoholysis of T8[OSiMe2H]g causes terminal Si-O bond... 

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