Organopolysilanes

Organometallic Nitrogen Compounds of Germanium, Tin, and Lead, 3, 397 Organometallic Pseudohalides, S, 169 Organometallic Reaction Mechanisms, 4, 267 Organopolysilanes, 6, 19... 

Numerous investigators followed the works of Yajima and Verbeek and started to explore the scope of melt spinnable organopolysilanes and organopolysilazanes for the preparation of ceramic fibers. 

Over the years since the publication of COMC II (1995), different aspects of organopolysilane chemistry have been reviewed in many book chapters and review articles, and these are noted in the text below. Wide coverage of the area was also given in a book published a few years ago with chapters contributed from many experts in the field.1... 

The currently accepted mechanism of the alkali metal-mediated Wurtz-type condensation of dichlorosilanes is essentially that outlined in COMC II (1995) (chapter Organopolysilanes, p 98) which derived from studies by Gautier and Worsfold,42 and the groups of Matyjaszewski43 and Jones,22,44,45 a modified polymerization scheme of which is included here. The mechanism was deduced from careful observations on the progress of polymerizations in different solvents (such as those which better stabilize anions and those which do not), at different temperatures,44 with additives, and with different alkali metal reductants. Silyl anions, silyl anion radicals,42 and silyl radicals28,46,47 are believed to be involved, as shown in Scheme 3. 

There is a brief reference to electroreductive silicon polymer formation in COMC II (1995) (chapter Organopolysilanes, p 96), but the very limited extent of the field at that time precluded further comment. Since then, the field has seen considerable progress, and the mild conditions have permitted the synthesis of functionalized polymers of moderate molecular weight (104), an example of which is the co-polymer poly(rncthyM-rncthoxymethoxyphcnylsilylene)-r -poly(methylphenylsilylene), 26, with a protected phenolic function, which was prepared with a molecular weight Mw= 19,000.96 Deprotection afforded the phenolic polymer. Several reviews on the area have been published.113-115... 

Several other synthetic techniques have also been described. Redistribution polymerization was outlined in COMC II (1995) (chapter Organopolysilanes, p 99) and proceeds by phosphonium salt-catalyzed redistribution of chlorodisilanes.133 Disproportionation polymerization, which is a similar process, has been described for the formation of polymers by ethoxide-catalyzed disproportionation of alkoxydisilanes via silyl anion intermediates.134 These procedures give rise to network polymeric products of rather low molecular weight (see below, Section 3.11.7.1). 

Functionalization of polysilanes by chemical modification (post-polymerization) was covered in COMC II (1995) (chapter Organopolysilanes, p 101), where the formation of precursor polysilanes with potentially functionalizable side groups such as chloride, type 34 (via HCI/AICI3 chlorodephenylation of PMPS), 6 triflate, type 35 (via triflate replacement of phenyl groups)135,137 or alkyl halide (via chloromethylation of phenyl groups,138,139 type 36, or addition of HC1 or HBr to double bonds140) was discussed. Four other precursor polysilanes, which utilize the reactivity of the Si-Cl or Si-H bond, have been successfully applied in functionalization since COMC (1995) perchloropolysilane, 17 (see Section 3.11.4.2.2.(i) for synthesis),103 poly[methyl(H)silylene-f >-methylphenylsilylene],... 

Harrod-type catalytic dehydrocoupling method using early transition metal catalysts (see COMC II (1995), chapter Organopolysilanes, p 99, and earlier in this review, Section 3.11.4.1.3. (i)).69,75 Si-H bonds are susceptible to free radical attack, and use of this was made in the free radical substitution of 38 to prepare a number of oxy-functionalized polysilanes, as shown in Scheme 25.185,186... 

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