Abstract
1H, 13C, 29Si, 77Se, 119Sn and 125Te NMR spectroscopies reveal that methyl, primary and secondary alkyl radicals, generated through the reaction of aryltelluroalkanes ( 4– 9) with tributyltin hydride, tributylgermanium hydride or tris(trimethylsilyl)silane) under standard radical conditions (benzene, AIBN) are capable of displacing tributylstannyl, tributylgermyl and tris(trimethylsilyl)silyl radicals from aryltellurotributylstannanes ( 1, 2), aryltellurotributylgermanes ( 10, 11) and aryltellurotris(trimethylsilyl)silanes ( 13, 14) respectively. These observations are in agreement with high-level ab initio molecular orbital studies. Calculations using a (valence) double- ζ pseudopotential basis set supplemented with polarization functions and with the inclusion of electron correlation (MP2/DZP) predict energy barriers for the displacement of stannyl (SnH 3), germyl (GeH 3) and trisilylsilyl ((H 3Si) 3)Si) radicals by methyl, ethyl and iso-propyl radicals to lie between 22 and 39 kJ mol −1, with reverse barriers of between 12 and 40 kJ mol −1. Consequently, the use of aryltellurides as alkyl radical precursors together with (standard) chain-carrying reagents such as tributyltin hydride, tributylgermanium hydride and tris(trimethylsilyl)silane may be complicated with equilibria which may result in diminished reaction yields.
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