Oxides silicon-phosphorus bonds

B. By oxidation Carbon-Phosphorus Bond Carbon-Silicon Bond Carbon-Halogen Bond Oxygen-Oxygen Bond Sulfur-Sulfur Bond... 

Oxidation of alcohol, carbonyl and acid functions, hydroxylation of aliphatic carbon atoms, hydroxylation of alicyclic carbon atoms, oxidation of aromatic carbon atoms, oxidation of carbon-carbon double bonds, oxidation of nitrogen-containing functional groups, oxidation of silicon, phosphorus, arsenic and sulfur, oxidative N-dealkylation, oxidative O- and S-dealkylation, oxidative deamination, other oxidative reactions... 

Olefin synthesis starts usually from carbonyl compounds and carbanions with relatively electropositive, redox-active substituents mostly containing phosphorus, sulfur, or silicon. The carbanions add to the carbonyl group and the oxy anion attacks the oxidizable atom Y in-tramolecularly. The oxide Y—O" is then eliminated and a new C—C bond is formed. Such reactions take place because the formation of a Y—0 bond is thermodynamically favored and because Y is able to expand its coordination sphere and to raise its oxidation number. 

Other theoretical studies discussed above include investigations of the potential energy profiles of 18 gas-phase identity S 2 reactions of methyl substrates using G2 quantum-chemical calculations," the transition structures, and secondary a-deuterium and solvent KIEs for the S 2 reaction between microsolvated fluoride ion and methyl halides,66 the S 2 reaction between ethylene oxide and guanine,37 the complexes formed between BF3 and MeOH, HOAc, dimethyl ether, diethyl ether, and ethylene oxide,38 the testing of a new nucleophilicity scale,98 the potential energy surfaces for the Sn2 reactions at carbon, silicon, and phosphorus,74 and a natural bond orbital-based CI/MP through-space/bond interaction analysis of the S 2 reaction between allyl bromide and ammonia.17... 

The main difference from C, N, and O is that Si, P, and S can form more bonds than the first row elements. This is because they have more orbitals the five 3d orbitals added to the 3s and three 3p orbitals. Silicon forms tetrahedral silanes, rather like alkanes, but also forms stable five-valent anions. Phosphorus forms phosphines, rather like amines, but also tetrahedral phosphine oxides. Sulfur can have any coordination number horn zero to seven, forming sulfides, like ethers, and tetrahedral sulfones with six bonds to sulfur. And it is with sulfur that we start. 

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