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On treatment of Na 2 B 6 H 6  with halogens in aqueous alkaline solution, the hexahalogenoborates B 6 X 6  2- , X = Cl, Br, I, are formed. Their octahedral structure is proved by  11 B NMR spectroscopy. The chemical shifts in relation to BF 3  · OEt 2  increase within the series H (-13.5) &lt; Cl (-17.4) &lt; Br (-18.5) &lt; I (- 27.5 ppm ). The IR and Raman spectra are assigned according to point group O h . The internal vibrations of the B 6 -cage, observed in the range 750-1250 cm -1  at nearly unchanged positions, are distinguishable from vibrations mainly originating from motions of the X 6 -shell against the rigid B 6 -cluster.

Darstellung, 11 B-NMR- und Schwingungsspektren der oktaedrischen closo-Boratanionen B 6 X 6 2- ; X = H, Cl, Br, I