| Oxidation of E-X bonds (E = Ge, Sn, Pb; X = R, ER3) with CB 11Me12· produces methyl-coordinated complexes of the corresponding Me3E+ cations with the CB11Me12− anion, with the free cation character increasing from Ge to Pb. For Si this oxidation results in a novel internally charge-compensated boronium ylid CB11Me 11, stable only below −60°C. By introducing solubilizing alkyl chains it is possible to obtain crystals of R3E+ cations, such as n-Bu3Sn+ CB11Me12−, whose structure reveals a tin cation weakly coordinated to methyl groups of two CB11Me 12− anions in a trigonal bipyramidal fashion. Oxidation of the stannylene [(Me3Si)2N],Sn: with the 1-R-CB 11Me11· radicals produces 1-R-CB 11Me11− salts of a cyclic stannylene with an ammonium nitrogen.;Acidolysis reactions of β-silylethyl acetates in solution were studied to understand processes that occur in a bilayer photoresist based on copolymers of poly(hydroxystyrene) and tris(trimethylsilyl)silylethyl methacrylate. Acid-catalyzed cleavage of the model trimethylsilylethyl acetate proceeds via a nucleophilic attack on the silicon atom of the protonated acetate. Protonation of β-tris(trimethylsilyl)silylethyl acetate is postulated to lead to a bridged siliconium cation, which reacts with nucleophiles, along three pathways and yields products in which a nucleophile is attached to either a carbon or a silicon atom. This mechanism is consistent with the observed silylation and alkylation of the phenolic hydroxyl groups in the photoresist film under photolithographic conditions.;An improved synthesis and a full characterization of all three 12-vertex C-hydroxydicarba-closo-dodecaboranes 1–3 are described. These inorganic phenols are moderately acidic, but unlike phertols, they are transparent in the near UV region and are stable to oxidation. Their oxyanions 1a–3a pose an interesting issue of a closo versus a bridged nido form. Also described is an introduction of a functionalized spacer in position 2 of 1 designed to permit incorporation into photoresists and other complex organic structures.;An approach to a new family of lithium ion conducting polymers based on the lithium salts of alkylated carboranyl CB11 anions is described. Preliminary results show that such materials can be made relatively easily and that they promise to provide superior solid polymer electrolytes. |
