32512-19-9Relevant academic research and scientific papers
Electron-induced dissociation of chlorosilanes: Role of aromatic side groups in gas phase and solution chemistry
B?hler,Postler,Gschliesser,Borrmann,Scheier,Denifl,Beckmann,Swiderek
, p. 169 - 176 (2014)
Dissociative electron attachment (DEA) to chlorotrimethylsilane (Me 3SiCl) and chlorodimethylphenylsilane (PhMe2SiCl) was studied to reveal a possible enhancing effect of the aromatic side group on the SiCl bond dissociation. Calculations point to a relevant interaction between the lowest unoccupied π* orbital of the phenyl ring and the σ*(SiCl) orbital and a consequent lowering of the lowest-energy electron attachment channel. It was previously reported that such a situation can lead to a significant enhancement of DEA. However, the lowest energy DEA channel in the investigated chlorosilanes lies below the thermodynamic limit for dissociation of the SiCl bond in the radical anion and thus cannot contribute to the Cl- yield. In consequence, release of chloride ions is in fact the dominant fragmentation channel but the Cl- yield is not noticeably enhanced in PhMe2SiCl. In contrast to the DEA results, comparative experiments on the reductive coupling in THF of Me3SiCl, PhMe2SiCl, and benzyldimethylchlorosilane (BzMe2SiCl) under identical conditions reveal a significant enhancement of the reactivity by aromatic side groups. As this finding does not correlate with the DEA results, an alternative explanation for the different reactivity of Me3SiCl and PhMe2SiCl in solution is suggested based on their vertical electron attachment energies and considering the impact of these quantities on the equilibrium between solvated electrons and neutral reactants on one side and the solvated radical anion on the other.
LASER-PHOTOLYSIS STUDY OF ARYL-SUBSTITUTED SILYL AND STANNYL ANIONS
Mochida, Kunio,Wakasa, Masanobu,Sakaguchi, Yoshio,Hayashi, Hisaharu
, p. 773 - 776 (2007/10/02)
Photochemical primary processes of aryl-substituted silyl and stannyl anions were studied at room temperature.The silyl and stannyl radicals generated were observed directly by laser-photolysis.
