Poly 7?- borane-derived

A. tris(Alkylamino)boranes-Derived Poly Z -(alkylamino)borazines]... 

As in the latter example, the same aminosilane employed for the synthesis of the disilaborane (Scheme 3.3-1) was used to incorporate a silicon vertex into a poly-borane cluster skeleton. However, attempts to use pentaborane(9) B5H9 for this method proved not to be successful. Instead, pentaborane(9) undergoes degradation and formation of the tetraborane derivative [B4H8SiMe(NMe2)2BH2] was observed [30],... 

Polymeric precursors have been developed which are stable at room temperature and when polymerized convert to ceramics in high yield. Such precursors may be synthesized by reaction of a vinylsilane, vinylmethylsilane, acetylene silane, or acetylene alkyl silane with a borane or a borane amine derivative The reactants are mixed in an inert atmosphere, either neat or in an aprotic solvent like acetonitrile, tetrahydrofuran, or a hydrocarbon, or in a mixture of such solvents. The reaction mixture is heated for 0.1 to 120 h at 90-170°C. The solvent, if any, is then removed. The polymer is pyrolyzed in argon or N2 at SOO-ISOO C for 1 h. BN and other ceramics such as B4C, or SipB QNs compounds can be made, where p, q, r, and s have various numerical values. To date, no measurements of the crystallographic form of the resultant BN compound have been made. Other precursors convertible to BN include poly (2-vinylpentaborane) oligomers. ... 

Poly(3-alkylthiophene)s are chemically robust, withstanding strong reductants including boranes [67] and LiAlH4 [72]. The electron-rich backbone is, however, readily functionalized by oxidative methods. Li and co-workers exploited this to replace the 4-proton with Cl, Br or NO2 functionality [73-75]. Reaction at the a-methylene was noted in some instances. Subsequent Pd-catalyzed cross-coupling of the perbrominated polymer could effect >99% derivatization. Oxidation renders the backbone susceptible to nucleophilic attack. Li et al. found that pyridine derivatives efficiently reacted at the 4-position of the radical cation, functionalizing up to 60 % of the putative polaron pentads. Use of l-methyl-4-(4 -pyridyl)pyridinium salts yielded viologen substituents [76]. 

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