Studies on tetraborane(8) carbonyl, B4H8·CO: its isomeric composition in the gas phase and in solution, and its reactions with alkenes1

Add time:08/19/2019    Source:sciencedirect.com

11B NMR spectra of tetraborane(8) carbonyl, B4H8·CO 1, reveal a changeover in the distribution of isomers in going from toluene solution to the gas phase. Fortuitously the distribution is 60:40 in each case, but comparison with published electron diffraction data and ab initio/IGLO computations indicates that the CO group is disposed endo with respect to the B4 `butterfly' framework in the predominant isomer in the gas phase, and exo in solution. The results also allow conclusions to be drawn about the geometries of other B4H8·L isomers on the basis of their reported proton NMR chemical shifts. Reactions of B4H8·CO with ethene and propene at ca. 30 bar yield products, R4B4H4·CO (R=Et 2 or Pr3 3), in which all four wingtip hydrogen atoms of the tetraborane carbonyl have been replaced by alkyl groups. Variable-temperature 11B and 1H NMR spectra of 2 and 3 reveal interesting fluxional behaviour.

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