Preparation and Chemistry of Me3SiCH2AsH2; Preparation of (Me3SiCH2(H)AsGaPh2)3, A Trimeric Mono(Arsino)Gallane Containing a Hydrogen Bonded to Arsenic. Isolation and X-Ray Crystal Structure of (Me3SiCH2As)5.

摘要

Reduction of Me3 SiCH2 AsCl2 (I) with LiALH4 at -78C afforded Me3SiCH2AsH2 (II), and reaction of II with Ph3Ga produced Me3SiCH2 (H) AsGaPh23 (III) which characterized by partial elemental analysis (C and H),1H NMR spectroscopy, and a cryoscopic molecular weight determination. Based on 1H NMR data, Me3SiCH2 (H) AsGaMe3 (IV) was produced by the reaction of II with Me3Ga; however, only H2 Me4Si, (Me3SiCH2As)5 (VI), and unreacted (Me3SiCH2)3 Ga were identified after allowing the latter to react with II. Reaction of two equivalents of Me3SiCl with a mixture of II and n-Buli (1:2 mole ratio) afforded Me3SiCH2As(SiMe3) 2 (V). The monosilylated arsine was not isolated when one equivalent of Me3SiCl was allowed to react with combined II and n Buli (1:1 mole ratio); rather, a mixture of II and V resulted. Attempted preparation of Me3SiCH2AsGaPH) (n) are described. The ring compound (Me3SiCH2As) 5 (VI) was prepared by reaction of Me3SiCH2AsCl2 with a mixture of Me3SiCl and Mg in THF. The molecular structure of this cycloarsane was determined by single-crystal X-ray diffraction methods. Keywords: Gallium-arsenic, Arsinogallane; Synthesis; Organoarsine; Cycloarsane; Crystal structure. (AW)