Vinylphosphine-borane: Synthesis, gas phase infrared spectroscopy, and quantum chemical vibrational calculations

Both experimental and theoretical investigations are reported on the infrared spectrum of vinylphosphine-borane (CH2=CHPH2 center dot BH3), a donor-acceptor complex. The gas phase infrared spectra (3500-600 cm(-1)) have been recorded at 0.5 cm(-1) resolution. This first primary alpha,beta-unsaturated phosphine-borane synthesized up to now is kinetically very unstable in the gas phase and decomposes rapidly into two fragments: the free vinylphosphine CH2=CHPH2 and the monoborane BH3 which dimerizes to form the more stable diborane B2H6. Spectra of free CH2 = CHPH2 and B2H6 compounds were also recorded to assign some vibration modes of the complex in very dense spectral regions. The analysis was completed by carrying out quantum mechanical calculations by density functional theory method at the B3LYP/6-31+G** level. Anharmonic frequencies and infrared intensities of the two predicted gauche and syn conformers of the vinylphosphine-borane complex were calculated in the 3500-100 cm(-1) region with the use of a variational approach, implemented in the P_ANHAR_V1.2 code. Because of the relatively weak interaction between the vinylphosphine and the monoborane, the vibrations of the complex can easily be subdivided into modes localized in the CH2= CHPH2 and BH3 moieties and into "intermolecular" modes. Localized modes are unambiguously correlated with the modes of the isolated monomers. Therefore, they are described in terms of the monomer vibrations, and the complexation shifts are defined as Delta nu=nu(complex)-nu(monomer) to make the effect of the complexation precise on each localized mode. In this objective, anharmonic frequencies and infrared intensities of the BH3 monomer and the stable gauche and syn conformers of the free vinylphosphine were obtained at the same level of theory. In the gas phase, only the syn form of the complex was observed and assigned. All theoretically predicted frequencies and complexation shifts in magnitude and direction are in good agreement with experiment. By infrared spectroscopy assisted by quantum chemical calculations, the consequences of the complexation of an alpha,beta-unsaturated phosphine by borane on the physicochemical properties of the formed 12-atom complex have been efficiently evaluated. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.3035902]