Vinyl radicals produced by annealing-induced reaction of mobilized hydrogen atoms with acetylene molecules in solid noble-gas matrices (Ar, Kr, and Xe) were characterized by Fourier transform infrared and electron paramagnetic resonance (EPR) spectroscopies. The hydrogen atoms were generated from acetylene by UV photolysis or fast electron irradiation. Two vibrational modes of the vinyl radical (nu7 and nu5) were assigned in IR absorption studies. The assignment is based on data for various isotopic substitutions (D and 13C) and confirmed by comparison with the EPR measurements and density-functional theory calculations. The data on the nu7 mode is in agreement with previous experimental and theoretical results whereas the nu5 frequency agrees well with the computational data but conflicts with the gas-phase IR emission results.

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The reaction of GeHal4 with MeN(CH2CH2OSiMe3)2 affords dihalogermocanes MeN(CH2 CH2O)2GeHal2 (1, Hal = Br; 2, Hal = Cl). Treatment of Me2Ge(NMe2)2 with MeN(CH2CH2OH)2 leads to dimethylgermocane MeN(CH2CH2O)2GeMe2 (3). The composition and structure of 1-3 were established by elemental analyses, 1H, 13C NMR spectroscopy, and mass spectrometry. The crystal structure of 1 is reported; structural data obtained from geometry DFT optimization on 1 are in good agreement with experimental results. Values of the electron density in the N→Ge bond critical point and the Laplacian of charge density for 1-3 indicate a closed-shell interaction between the Ge and N atoms.

This paper addresses the basic question of the impact of a chemically inert environment on the radiation-induced transformations of isolated organic molecules in icy media at cryogenic temperatures with possible...

Antimony tris‐amides — (Et2N)3−nSb[N(C6F5)(2‐C5H4N)]n [n = 1 (3), 2 (4) or 3 (5)] — have been prepared by treatment of Sb(NEt2)3 (1) with stoichiometric amounts of (2‐C5H4N)(C6F5)NH (2). In contrast to amide 5, compounds 3 and 4 are unexpectedly unstable and react further to give the bis‐amido antimony fluorides [(2‐Et2N‐C6F4)(2‐C5H4N)N]Sb(F)[N(C2H5)2] (6) and [(2‐Et2N‐C6F4)(2‐C5H4N)N]Sb(F)[N(C6F5)(2‐C5H4N)] (7). The structure of 7 was confirmed by X‐ray diffraction studies. DFT calculations, which reproduce the principal features of compound 7’s geometry, have been used to explain the possible reaction pathway of this ortho‐directed metathetical fluoride‐amide exchange. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)