abstract45
Paper
J. Chem. Soc., Dalton Trans., 2002, 2624 – 2631, DOI: 10.1039/b200930g
A convenient cyanide-free one-pot synthesis of nido-Me3N-7-CB10H12 and nido-7-CB10H13–
Andrei S. Batsanov, Mark A. Fox, Andrés E. Goeta, Judith A. K. Howard, Andrew K. Hughes and John M. Malget
Reaction of nido–tBuH2N-7-CB10H12 with Na2CO3 and (MeO)2SO2 in THF results in mono-methylation to give nido–tBuMeHN-7-CB10H12, whilst prolonged reaction at elevated temperatures results in a quantitative yield of the tri-methyl derivative nido-Me3N-7-CB10H12, as a result of metathesis of the tert-butyl group. The 11B NMR spectrum of nido–tBuMeHN-7-CB10H12 is explored as a function of pH, demonstrating exchange with nido–tBuMeN-7-CB10H12–. Reaction of B10H14 with CyNC gives nido-CyH2N-7-CB10H12, which is methylated by Na2CO3 and (MeO)2SO2 in THF to give nido-CyMe2N-7-CB10H12. Deprotonation of nido-Me3N-7-CB10H12 and nido-CyMe2N-7-CB10H12 yields Na[nido-Me3N-7-CB10H11] and Na[nido-CyMe2N-7-CB10H11] respectively. Both trialkyl(amino)carboranes can be converted to Na[nido-CB10H13], itself a precursor to the poorly coordinating anion closo-CB11H12–. The molecular structures of nido–tBuMeHN-7-CB10H12 and nido-CyMe2N-7-CB10H12, determined by single crystal X-ray diffraction, are reported.
