Mass spectrometric evidence for collisionally induced removal of H(2) from monoanions of (10)B nido-carborane derivatives investigated by electrospray ionization quadrupole linear ion trap and Fourier transform ion cyclotron resonance mass spectrometry.

Some newly synthesized (10)B nido-carborane derivatives, i.e., 7,8-dicarba-nido-undecaborane monoanions (7-Me-8-R-C(2)B(9)H(10)K(+), R = H, butyl, hexyl, octyl and decyl), have been fully characterised and examined by electrospray ionization and Fourier transform ion cyclotron resonance mass spectrometry with liquid chromatographic separation (LC/ESI-FTICR-MS). These boron-containing compounds exhibit abundant molecular ions (M) at m/z 140.22631 C(3) (10)B(9)H(14), m/z 196.28883 C(7) (10)B(9)H(22), m/z 224.32032 C(9) (10)B(9)H(26), m/z 252.35133 C(11) (10)B(9)H(30) and m/z 280.38354 C(13) (10)B(9)H(34) at the normal tube lens voltage setting of -90 V, which was an instrumental parameter value selected in the tuning operation. Additional M-nH(2) (n = 1-4) ions were observed in the mass spectra when higher tube lens voltages were applied, i.e., -140 V. High-resolution FTICR-MS data revealed the accurate masses of fragment ions, bearing either an even or an odd number of electrons. Collision-induced dissociation of the M-nH(2) ions (n = 0-4) in the quadrupole linear ion trap (LTQ) analyzer confirmed the loss of hydrogen molecules from the molecular ions. It is suggested that the loss of H(2) molecules from the alkyl chain is a consequence of the stabilization effect of the nido-carborane charged polyhedral skeleton.