title: Structural effect on the stability of acetophenone-B(OMe)2 complexes in the gas phase. The nature of the bond between the boron cation and neutral molecules.
abstract: The free energy changes (DeltaG, boron cation basicity; BCB) for the reaction [(MeO)2B]L+ = (MeO)2B+ + L (L = acetophenones) were determined in the gas phase by measuring ligand exchange equilibria using an FT-ICR mass spectrometer. On the basis of the correlation analysis by the Yukawa-Tsuno equation, DeltaG = rho(sigma degrees + r+DeltasigmaR+), the substituent effect on DeltaBCB of acetophenone was characterized by a rho value (in kJ mol(-1) sigma(-1) unit) of -43.2 and an r+ value of 0.89. Both the rho and r+ values were found to be similar to the corresponding values for protonation, indicating that the bond between (MeO)2B+ and the oxygen atom of the carbonyl group has a high covalent character similar to the H+-O=C bond. This conclusion was consistent with the geometrical features and the charge distribution calculated at DFT-B3LYP/6-311+G(d,p) level of theory. A comparison with the results for a series of Lewis cation basicity of the acetophenone system showed that the r+ value decreases in the order of H+ = (MeO)2B+ > Me3Si+ > Me3Ge+ > Cu+ > Li+. This decreasing order is related to increasing ionic (ion-dipole interaction) nature of the bonding interaction between Lewis cations and the carbonyl oxygen atom. This was also supported by the theoretical calculations.
authors.affiliation: Department of Chemistry and Physics of Condensed Matter, Graduate School of Sciences, Kyushu University, Hakozaki, Higashi-ku, Fukuoka, 812-8581, Japan.
authors.forename: Shuhei
authors.initials: S
authors.lastname: Itoh
authors.forename: Md Mizanur Rahman
authors.initials: MM
authors.lastname: Badal
authors.forename: Masaaki
authors.initials: M
authors.lastname: Mishima