Four different carboranethiol derivatives were used to modify the surfaces of gold nanoparticles and flat gold films. The novel materials engendered from these modifications are extraordinarily stable species with surfaces that support self-assembled monolayers of 1-(HS)-1,2-C2B10H11, 1,2-(HS)2-1,2-C2B10H10, 1,12-(HS)2-1,12-C2B10H10, and 9,12-(HS)2-1,2-C2B10H10, respectively. Surprisingly, characterization of these materials revealed that a number of molecules of the carboranethiol derivatives are incorporated inside the nanoparticles. This structural feature was studied using a number of techniques, including X-ray photoelectron spectroscopy (XPS), UV-vis, and IR spectroscopies. Thermal desorption experiments show that carborane molecules detach and leave the nanoparticle surface mostly as 1,2-C2B10H10 isotopic clusters, leaving sulfur atoms bound to the gold surface. The surfaces of both the gold nanoparticles and the flat gold films are densely packed with carboranethiolate units. One carborane cluster molecule occupies an area of six to seven surface gold atoms of the nanoparticle and eight surface gold atoms of the flat film. XPS data showed that molecules of 1,12-(HS)2-1,12-C2B10H10 bind to the flat gold surface with only half of the thiol groups due to the steric demands of the icosahedral carborane skeleton. Electrochemical measurements indicate complete coverage of the modified gold surfaces with the carboranethiol molecules.

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Deamination of 7-(Me3N)-nido-7,8,9-C3B8H10 (1a) leads either to the parent tricarbollide anion [nido-7,8,9-C3B8H11]- (2 - ) or to the neutral tricarbaborane nido-7,8,9-C3B8H12 (2a), together with a small amount of 8-Me-nido-7,8,9-C3B8H11 (2b). Di- and trisubstituted derivatives of 2a, 7-(Bu t MeN)-10-Me-nido-7,8,9-C3B8H10 (2c), and 7-(Bu t MeN)-10,11-Me2-nido-7,8,9- C3B8H9 (2d) were obtained as byproducts from the methylation of both 7-(Bu t NH2)-nido-7,8,9-C3B8H10 (1b) and 7-(Bu t MeNH)-nido-7,8,9- C3B8H10 (1c) with MeI in THF under reflux. Heating of 1a and 2 - at 350 °C resulted in the rearrangement of the carbons on the open-face to give high yields of the isomeric tricarbollides 10-(Me3N)-nido-7,8,10-C3B8H10 (3a) and [nido -7,8,10-C3B8H11]- (4 - ), respectively. The structure of 3a was determined by an X-ray diffraction analysis, and the geometries of the parent compounds 2 - , 2a, and 4 - were optimized at the ab initio MP2(fc)/6-31G* level. The structures of all compounds also were secured by the excellent agreement between the experimental data and the IGLO/NMR calculations of the 11B chemical shifts for the parent compounds at the DZ//6-31G*, DZ//MP2/6-31G*, and II‘//MP2/6-31G* levels.