The acidity of polyhalogenated silanes and silyl radicals

Abstract

The results of abinitio molecular orbital calculations at the MP4SDTQ/6-31++G(d,p)//HF/6-31++G(d,p) level have been used to calculate acidities of fluoro- and chloro-substituted silanes and silyl radicals. The radicals are more acidic than the silanes and substituent effects are also slightly larger in the radicals. For the gas phase deprotonation of fluorosilanes at 298 K, ΔHr (kcal/mol) values are SiH4, 378.5; SiH3F, 374.5; SiH2F, 366.7, and SiHF3, 351.0, i.e., interaction between fluorine atoms leads to increased enhancement of acidity. For chlorosilanes substituent effects are larger but strictly additive (13 kcal/mol for each Cl atom) with ΔHr values SiH3Cl, 365.4; SiH2Cl2 352.5, and SiHCl3 339.4. The electron affinities of silyl radicals calculated using isogyric reactions at the MP4SDTQ/6-31++G(d,p) level are too low by ~0.3 eV, but at the MP4SDTQ/6-311++G(2df,p) level the calculated electron affinity of SiH3 is 1.39 eV, compared with an experimental value of 1.44 ± 0.03 eV. This higher level of theory gives calculated electron affinities of 1.53 eV for SiH2F and 1.92 eV for SiH2Cl. Heats of formation obtained by using isogyric reactions to calculate atomization energies at the MP4SDTQ/6-311++G(2df,p) level are within 3 kcal/mol of experimental values except for SiH2F (where the "experimental" value was obtained from linear interpolation between SiH3 and SiF3). [Formula: see text] (kcal/mol) calculated for the anions are SiH3−, 14.4; SiH2F−, −78.0; and SiH2Cl−, −37.6.