109997-41-3Relevant academic research and scientific papers
Reactions of (Me3SiCH2)2AsSiMe3 with gallium halides. Crystal structure and dynamic NMR study of the dimer {[(Me3SiCH2)2As]2GaBr}2
Purdy, Andrew P.,Wells, Richard L.,McPhail, Andrew T.,Pitt, Colin G.
, p. 2099 - 2105 (1987)
(Me3SiCH2)2AsSiMe3 reacted with the gallium halides GaBr3, MeGaCl2, and PhGaCl2 to produce the (arsino)gallanes [(Me3SiCH2)2AsGaBr2]3, {[(Me3SiCH2)2As]2GaBr}2, [(Me3SiCH2)2AsGaMeCl]n (n = 2, 3), and [(Me3SiCH2)2AsGaClPh]n (n = 2, 3), which were characterized by elemental analysis (C and H), 1H and C NMR spectroscopy, and cryoscopic molecular weight determinations. A single-crystal X-ray diffraction study of {[(Me3SiCH2)2As]2GaBr}2 was carried out. Crystal data are as follows: triclinic, space group P1, a = 11.892 (2) ?, b = 12.492 (2) ?, c = 11.515 (1) ?, α = 98.24 (1)°, β = 113.57 (1)°, γ = 84.21 (1)°, V = 1549.9 ?3, Z = 1. The centrosymmetric, dimeric molecule crystallizes in the trans configuration, with unequal endocyclic Ga-As distances [2.513 (1) ? and 2.521 (1) ?] and very significantly different bond angles [84.37 (1)° and 95.63 (2)°, respectively, at Ga and As] in the planar (Ga-As)2 ring. The Ga-exo-As distance of 2.437 (1) ? is the shortest yet measured in an organogallium-arsenic compound. A 13C{1H} dynamic NMR study of {[(Me3SiCH2)2As]2GaBr}2 revealed that both an interchange of the (Me3SiCH2)2As groups [ΔH? = 18.7 ± 0.3 kcal/mol; ΔS? = 4.5 ± 1.0 cal/(mol K)] and a trans-cis isomerization [ΔH? = 17.4 ± 0.7 kcal/mol; ΔS? = -2.2 ± 2.1 cal/(mol K)] take place.
