Search

By reaction of Na2[B9H9] with the appropriate N-halogenosuccinimide, the monohalogenated anion [1-XB9H8]2- (X = Cl, Br, or I) is formed. The X-ray diffraction analyses performed on single crystals of (Ph4P)2[1-XB9H8].CH3CN (X = Cl, Br, I) reveal that the tricapped trigonal prismatic geometry of the cluster is retained after substitution in the 1-position. Crystallographic data are as follows for (Ph4P)2[1-XB9H8].CH3CN. X = Cl, Br: monoclinic, space group P2(1), a = 10.7 A, b = 32.9 A, c = 13.8 A, beta = 96 degrees, Z = 4, R1 = 0.038 and R1 = 0.036, respectively. X = I: monoclinic, space group P2(1)/n, a = 10.5 A, b = 13.6 A, c = 33.4 A, beta = 94 degrees, Z = 4, R1 = 0.094. The compounds have been characterized by vibrational and 11B NMR spectroscopy as well.

Monoanionic hexaborate cluster radicals [B(6)Hal(n)()Hal'(6)(-)(n)()](*)(-) with mixed halogen substitution were prepared from oxidizable dianionic precursors and were characterized by vibrational and UV-vis spectroscopy. EPR studies of these and the structurally established homoleptic species [B(6)Hal(6)](*)(-) (Hal = Cl, Br, I) reveal strongly increasing g anisotropy and relaxation rate on replacing Cl by Br and especially I substituents; the very stable B(6)I(6)(*)(-) ion (g(1) = 2.04, g(2) = 1.66, g(3) = 1.15) thus exhibits an EPR spectrum only at 4 K. The extent of these effects is attributed to the Jahn-Teller situation in [B(6)X(6)](*)(-) with only partial occupancy of a degenerate MO. Both the absence of B-H bonds and the evidently strong participation of the halogen substituents in the singly occupied MO contribute to the extraordinary stability of these cluster radicals.