RESUMO
Reactions of ß-diketiminato alkaline earth alkyldiboranate derivatives [(BDI)Ae{pinBB(R)pin}] (BDI = HC{(Me)CNDipp}2; Dipp = 2,6-i-Pr2C6H3; Ae = Mg, R = n-Bu or Ae = Ca, R = n-hexyl) with t-BuNC provide access to the respective group 2 derivatives of unprecedented diborata-allyl, {(pinB)2CNBpin(t-Bu)}-, anions. Although the necessary mode of B-C bond cleavage implicated in these transformations could not be elucidated, further studies of the reactivity of magnesium triboranates toward isonitriles delivered a more general and rational synthetic access to analogous anionic moieties. Extending this latter reactivity to a less symmetric triboranate variant also provided an isomeric Mg-C-bonded dibora-alkyl species and sufficient experimental insight to prompt theoretical evaluation of this reactivity. DFT calculations, thus, support a reaction pathway predicated on initial RNC attack at a peripheral boron centre and the intermediacy of such dibora-alkyl intermediates.
RESUMO
A series of complexes generated through reactions of the ß-diketiminato magnesium diboranate species, [(BDI)Mg{(n-Bu)pinB-Bpin}] (BDI = HC{(Me)CNDipp}2; Dipp = 2,6-di-iso-propylphenyl), and a variety of organic nitriles are reported. Although, in every case, the diboranate anion acts as a surrogate source of the {Bpin} nucleophile, resulting in B-C bond formation at the electrophilic sp-hydridised nitrile carbon, the resultant compounds display a variable propensity to undergo subsequent reaction with additional nitrile equivalents. This behaviour is rationalised to be a consequence of substituent-dependent modulation in the basicity and resultant electrophilicity of magnesium-coordinated nitrile intermediates.
RESUMO
The effect of thermal treatment on the structure and electrical/optical properties of vapor phase-polymerized poly(3,4-ethylenedioxythiophene):tosylate (PEDOT:Tos) and polypyrrole:tosylate (PPy:Tos) polymer films was investigated. Thermal treatment was applied postpolymerization but prior to washing the embedded oxidant layer out of the polymer film. Structural and chemical changes arising from the treatment were studied in the context of their conductive and electrochromic behavior. Spectroscopic analysis indicated a rise in the doping levels of both conductive polymers when exposed to thermal treatment. Additionally, an increase in the film thickness was recorded after the oxidant and other unbound species were removed from the polymer layer using an ethanol rinse. As such, a strong indication that polymerization continued even in the absence of (external) monomer vapor was present. This film thickness increase was most pronounced for PPy:Tos but also present in the PEDOT:Tos film. Heat-treated films exhibited enhanced cohesion, making them more robust and therefore increasing the viability for the material to be used in the optoelectronics area. This robustness, due to additional (cross-linking) oligomer growth, came at the expense of lower conductivity relative to their untreated counterparts.
