Darstellung, Schwingungsspektren und Normalkoordinationsanalyse der D- und 13C-Isotopomeren des Methylpentahydro-closo-hexaborats [B6H5(CH3)]2- sowie Kristallstruktur von [P(C6H5)4][B6H6(CH3)] / Preparation, Vibrational Spectra and Normal Coordinate Analysis of the D and 13C Isotopomeres of the Methylpentahydro-closo-hexaborate [B6H5(CH3)]2- and the Crystal Structure of [P(C6H5)4][B6H6(CH3)

Abstract

The crystal structure of [P(C6H5)4][B6H6(CH3)] has been determined by single crystal X-ray diffraction analysis; triclinic space group P 1̄ with a = 7.408(2), b = 11.887(3), c = 14.4486(9) Å , α = 80.013(12), β = 79.421(10), γ = 88.85(2)°. The additional H atom could be refined with B - H distances between 1.21 and 1.31 Å above one of the facettes of the B6 octahedron adjacent to the methyl group. The IR and Raman spectra of the ueprotonated Cs salts of the six isotopomers [B6H5(CH3)]2-, [B6H5(CD3)]2-, [B6H5(13CH3)]2-, [B6D5(CH3)]2-, [B6D5(CD3)]2- and [B6D5(13CH3)]2- exhibit characteristic shifts of their vibration bands. Using the crystallographic data a normal coordinate analysis has been performed, based on a general valence force field. With a set of 14 force constants (e.g. fd(BB ) = 1.80, fd(BC ) = 3.70, fd(BH ) = 3.17, fd(CH ) = 4.62 mdyn/Å) good agreement between observed and calculated frequencies o f all D and 13C isotopically labeled derivatives has been achieved. The potential energy distribution on the force constants reveals strong vibrational couplings of the boron cage with the substituents. The B - C stretching vibration o f the CH3 group is observed in the region 1142-1153 cm-1, for the CD3 substituent at higher frequencies of 1168-1179 cm-1.