Synthesis and characterization of new 19-vertex macropolyhedral boron hydrides

The new boron hydride anions 10-R-B19H19- (R = H, Thx) were synthesized by the reaction of M2[B18H20] (M = Na, K) with HBRCl.SMe2 (R = H, Thx) or HBCl2.SMe2 in diethyl ether. The anions are comprised of edge-sharing, nido 10- and 11-vertex cluster fragments, and are characterized by their 11B, 11B[1H], and 11B-11B COSY NMR spectra. The salt [(Ph3P)2N][B19H20].0.5THF crystallized in the triclinic space group P1 (a = 12.6344-(2) A, b = 13.5978(2) A, c = 14.1401(2) A; alpha = 77.402(2) degrees, beta = 81.351(2) degrees, gamma = 73.253(2) degrees). Possible synthetic pathways are discussed. The dianion B19H19(2-) is formed by deprotonation of B19H20- with Proton Sponge (1,8-bis(dimethylamino)naphthalene) in THF, and is identified on the basis of its 11B, 11B[1H], and 11B-11B COSY NMR spectra.