Organosilicon reactivity

Organosilicon compounds receive attack of nucleophilic, electrophilic, and homolytic reagents. The latter is related to the formation of radicals and divalent species. Organosilicon reactive intermediates corresponding to free radicals, carbenium ions, carbanions, and carbenes play important roles in these reactions. These are sUyl radicals, silylium... 

Brook, A. G. Bassindale, A. R. In Organic Chemistry DeMayo, R, Ed. Academic New York, 1980 Vol. 2, Essay No. 9. This article is the only comprehensive review of organosilicon rearrangements and suffers only from being a bit dated and its total exclusion of the rearrangements of organosilicon reactive intermediates. 

H. Sakurai (ed.), Organosilicon and Bioorganosilicon Chemistry—Structure, Bonding, Reactivity, and Synthetic Application. Ellis Horwood. Chichester, 1985. 

In this section, the reactivities of organosilicon compounds for the Friedel-Crafts alkylation of aromatic compounds in the presence of aluminum chloride catalyst and the mechanism of the alkylation reactions will be discus.sed, along with the orientation and isomer distribution in the products and associated problems such as the decomposition of chloroalkylsilanes to chlorosilanes.. Side reactions such as transalkylation and reorientation of alkylated products will also be mentioned, and the insertion reaction of allylsilylation and other related reactions will be explained. 

II. Subvalent and Unsaturated Organosilicon Compounds Formation and Reactivity... 

Summary The formation, reactivity, and cycloaddition behavior of neopentylsilenes towards suitable reaction partners is described. Especially l,l-dichloro-2-neopentylsilene. Cl2Si=CHCH2Bu (2) - easily obtained from vinyltrichlorosilane and LiBu - is a useful building block for the synthesis of SiC four membered ring compounds. These can be converted into the isomeric Diels-Alder and retro ene products upon thermolysis reactions. The mode of the silenes cycloaddition reactions ([4+2] vs [2+2] addition) can be directed by either the substitution pattern at the Si=C moiety, the choice of reaction partners or the conditions. Furthermore the products resulting from cycloaddition reactions open up a wide variety of following reactions, which possibly will lead to new organosilicon materials or pharmaceutical compounds. 

Organogermanium compounds resemble their organosilicon analogues in their reactivity in crosscoupling reactions, and require nucleophilic activation (Section 9.6.3.2 2)... 

It is necessary for the intermediate cation or complex to bear considerable car-bocationic character at the carbon center in order for effective hydride transfer to be possible. By carbocationic character it is meant that there must be a substantial deficiency of electron density at carbon or reduction will not occur. For example, the sesquixanthydryl cation l,26 dioxolenium ion 2,27 boron-complexed imines 3, and O-alkylated amide 4,28 are apparently all too stable to receive hydride from organosilicon hydrides and are reportedly not reduced (although the behavior of 1 is in dispute29). This lack of reactivity by very stable cations toward organosilicon hydrides can enhance selectivity in ionic reductions. 

Chemical reactivity of unfunctionalized organosilicon compounds, the tetraalkylsilanes, are generally very low. There has been virtually no method for the selective transformation of unfunctionalized tetraalkylsilanes into other compounds under mild conditions. The electrochemical reactivity of tetraalkylsilanes is also very low. Kochi et al. have reported the oxidation potentials of tetraalkyl group-14-metal compounds determined by cyclic voltammetry [2]. The oxidation potential (Ep) increases in the order of Pb < Sn < Ge < Si as shown in Table 1. The order of the oxidation potential is the same as that of the ionization potentials and the steric effect of the alkyl group is very small. Therefore, the electron transfer is suggested as proceeding by an outer-sphere process. However, it seems to be difficult to oxidize tetraalkylsilanes electro-chemically in a practical sense because the oxidation potentials are outside the electrochemical windows of the usual supporting electrolyte/solvent systems (>2.5 V). 

The chemistry of compounds containing Si-Si bond(s) is an intriguing subject in the field of organosilicon chemistry because Si-Si bonds have unique physical and chemical properties. The reactivities of Si-Si bonds is often compared with those of carbon-carbon double bonds. The current interest in polysilanes in material science stems from the fact that they exhibit unusual properties implying considerable electron delocalization in the polymer chain [62]. This section concerns with the unique elecrochemical properties of compounds containing Si-Si bonds (Sect. 2.4). 

There is a current drive in microlithography to define submicron features in bilevel resist structures. The introduction of organometallic components, most notably organosilicon substituents, into conventional resists is one promising approach. To this end, organosilicon moieties have been primarily utilized in starting monomers (1-4) or in post-polymerization functionalization reactions on the polymer (5,6). Little work has been done on the reaction of preformed reactive oligomers to synthesize block copolymer systems. 

Although carbon and silicon both belong to the same group of periodic table and many of the silicon compounds resemble carbon compounds, but the chemical reactivity of silicon in organosilicon compounds is more comparable to that of hydrogen because many nucleophilic displacements at... 

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