Metal silicon—oxygen bonds

A high degree of hydrophobic character is an almost unique characteristic of silicon-rich or pure-silica-type microporous crystals. In contrast to the surface of crystalline or amorphous oxides decorated with coordinatively unsaturated atoms (in activated form), the silicon-rich zeolites offer a well-defined, coordinatively saturated sur ce. Such surfrces, based on the strong covalent character of the silicon-oxygen bond and the absence of hydrophilic centers, display a strong hydrophobic character unmatched by the coordinativeiy unsaturated, imperfect surfaces. Also, hydrophobic zeolite crystals have been reported to suppress the water affinity of transition metal cations contained in the zeolite pores. This property permits the adsorption of reactants such as carbon monoxide or hydrocarbons in the presence of water. 

The hydrosilylation of carbon-heteroatom multiple bonds had received little attention until it was found in 1972 that Rh(PPh3)3Cl is an extremely effective catalyst for the hydrosilylation of carbonyl compounds. This is a new and unique reduction method since the resulting silicon-oxygen bond can easily be hydrolyzed. Other transition metal complexes including platinum, ruthenium , and rhodium also have good catalytic activity in the selective and asymmetric hydrosilylation of carbonyl compounds "". 

A typical absorption curve obtained for a metal-free vitreous silica after a large dose of y-rays is shown in Figure 13. The main band is at 215 nm three smaller bands occur at 230, 260, and 280 nm. The 230-nm band may result from an electron trapped at a silicon atom having an incomplete oxygen bond (205). 

When the counterion is varied from lithium to sodium to potassium, the proportion of inversion increases. The relatively covalent lithium-oxygen bond favours a retentive mechanism. However, as the metal-oxygen bond becomes more ionic, the components may function more independently, allowing attack of RO on the back face of the silicon tetrahedron while electrophilic assistance by M+ of the leaving group aids inversion of configuration. 

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