Polymer-silylamide

As noted above, KH-catalyzed polymerization of the CH3SiHCl2 ammonolysis product gives a polymeric silylamide of type [(CH3SiHNH)a-(CH3SiN)b(CH3SiHNK)e]. In a typical example, a = 0.39, b = 0.57, c = 0.04, so there is only a low concentration of silylamide functions in the polymer. This polymeric silylamide reacts with electrophiles other than... 

In an attempt to prepare polymers of type Ic or Id from acid amides and 1,3-dichlorodisiloxanes or 1,5-dichlorotrisiloxanes, it was found that bimolecular cyclization prevailed over polycondensation and cyclic bis(silylamides) in the amido (la) or imidato (lb) isomeric forms were exclusively formed in high yields... 

Lanthanum dibenzyl complexes with triazanonane-silylamide, amidine and 1,3-diketiminate monoanionic ancillary ligands were also prepared by in situ peralkylation in the presence of the protonated ligand or by com-plexation (for 1,3-diketiminate) with lanthanum tribromide and subsequent alkylation. The coordination polymer [p-r 2 r 1-ArNC(Me)CHC(CH2)-NAr]2La[K(THF)4] n formed by H-abstraction from one of the diketimi-nate Me groups and a ligand redistribution.14... 

Treatment of the phosphine resin 33 with alkyl bromides, e.g. 34, gave the corresponding phosphonium bromide 35 in excellent yields. The formation of the phosphorane was described as a cmdal step, for which the transport of the base to the phosphonium site within the polymer was essential. Various bases, such as sodium hydride, potassium tert-butoxide in THF, and n-butyllithium in dioxane, have been employed. Good results for the formation of the ylide were obtained with a mixture of sodium methoxide, methanol, and THF, and more recently with sodium bis(trimethyl)silylamide in THF [34, 35]. After the addition of aldehyde 36... 

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