Abstract

By reaction of [B6H6]2- with dibenzoylperoxide in dichloromethane conjuncto-[B6H6- B6H6]2- is formed. The product could be separated from excess [B6H6]2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of [P(C6H5)4]2 -conjuncto- [B6H6-B6H6] has been determined by single crystal X-ray diffraction analysis; triclinic, space group P1̄ with a = 10.8315(10), b = 11,2422( 12), c = 20.340(2) Å, α = 91.278° (9), β = 90.178° (9), γ = 105.662°(9). The 11B NMR spectrum reveals three signals with the intensity ratio 1:1:4, for two equivalent moieties of the conjuncto molecule ion with local C4v symmetry. The IR and Raman spectra of the deprotonated Cs salts of the 10B, 11B and their respective D isotopomers of conjuncto-[B6H5-B6H5]4- exhibit characteristic shifts. Using averaged crystallographic data and assuming idealized D4h symmetry, normal coordinate analyses have been performed based on a modified valence force field. With a set of eleven force constants (e.g. fd(BB)conjuncto = 2.9, fd(BB)cage = 1.6 mdyn/Å) very good agreement between observed and calculated frequencies has been achieved. From strong vibrational coupling with the B6 clusters two vibrations result for the conjuncto B-B bond at 1142/1198 and 292/304cm-1 for 11B/10B species, respectively. They can be assigned as anti-phase and in-phase motions of the conjuncto B atoms related to the equatorial B4 planes.

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