Quantumchemical investigation of borabenzene adduct with pyridine

Corrigendum to: Quantum-chemical Ab Initio Calculations on the Donor–Acceptor Complex Pyridine–Borabenzene (C5H5N–BC5H5)

“…[11] The calculated N-B distances of 1.551 (TZ2P plus thermal correction/6-311þþG**) and 1.566 Å (CISD/6-311þþG**) are also close to that of 1.558(3) Å obtained by single-crystal X-ray diffraction. [2] Moreover, at 120.68, the C-B-C angle is also quite similar to the experimental value of 119.1(2)8 in the solid state.…”

“…A somewhat less negative value of À46.4 kcal mol À1 was obtained in the DFT study by Semenov and Sigolaev mentioned above. [11] All these energies of reaction are similar in that the change of energy on formation of the borabenzenepyridine complex from borabenzene and pyridine slightly exceeds three times the value of À14.9 kcal mol À1 calculated for the formation of C 5 H 5 B-N 2 from borabenzene and dinitrogen (CCSD(T)aug-cc-pVTZ//TZ2P plus thermal correction/-311þþG**). [12] The calculated reaction energies for the formation of 1 from its constituents are, therefore, comparable with the negative of the bond energy of Cl 3 Al-NMe 3 (À49.3 kcal mol À1 ), z the most strongly bonded donor-acceptor complex studied by Jonas et al [16] According to a natural population analysis, formation of 1 from borabenzene and pyridine goes in parallel with a charge transfer of 0.33 e from the C 5 H 5 N to the C 5 H 5 B unit.…”

“…Those calculations were performed with the PPP and the CIS CNDO/S method respectively, [2,11] and the outcome of these calculations borabenzene from the cited literature Wavelengths (l max ) in nm. Oscillator strengths for the calculated transitions and extinction coefficients for the experimental data are given in parentheses; PPP, Pariser-Parr-Pople; CIS CNDO/S, configuration interaction including single excitations employing the spectroscopic complete neglect of differential overlap approximation Experimental [2]A PPP [2] CIS CNDO/S [11] 472 (2825) and CAM-B3LYP (solid) functional employing: (a) the B3LYP/6-311þþG (3df,3pd); and (b) the aug-cc-pVDZ basis set. All calculations were performed using the MP2/6-311þþG**-optimized structures (l in nm, e in 1000 cm 2 mol À1 ).…”

“…A similarly strong solvent dependence of this band was obtained by an electrostatic solvent model in combination with the semi-empirical configuration interaction including single excitations employing the spectroscopic complete neglect of differential overlap approximation (CIS CNDO/S) method. [11] Moreover, in further characterizing the compound, Boese et al [2] reported intense absorptions in the infrared at ,1500 and ,700 cm À1 .…”

“…Borabenzene (C 5 H 5 B) has been the subject of some experimental [1][2][3] and an even higher number of theoretical [4][5][6][7][8][9][10][11][12] studies; however, attempts to generate the free compound have met with failure so far. At least in two experimental studies, borabenzenze apparently occurred as a transient that was trapped either by dinitrogen [1] or pyridine.…”