Experimental and Theoretical Studies of Co(CH_4)_x^+ with x = 1-4
Chris L. Haynes, P. B. Armentrout, Jason K. Perry, William A. Goddard III
Abstract
The sequential bond energies of Co(CH_4)_x^+, x = 1-4, are determined experimentally and theoretically. Collision-induced dissociation studies conducted using a guided ion beam tandem mass spectrometer yield 0 K bond energies of D_o[Co^+-Xe] = 0.85 ± 0.07 eV, D_o[Co^+-CH_4] = 0.93 ± 0.06 eV, D_o[Co(CH_4)^+-CH_4] = 1.00 ± 0.05 eV, D_0[Co(CH_4)_2^+-CH_4] = 0.41 ± 0.05 eV, and D_o[Co(CH-4)_3^+-CH_4] = 0.67 ± 0.06 eV. These numbers are in excellent agreement with ab initio calculations which lead to values of D_e[Co^+-(CH_4)] = 0.93 eV, D_e[Co(CH_4)^+-CH_4] = 1.00 eV, D_e[Co(CH_4)_2+-CH_4] ≈ 0.40 eV, and D_e[Co(CH_4)_3^+-CH_4] ≈ 0.70 eV. We find that the nonmonotonic behavior in the sequential binding energies arises from changes in hybridization at the metal center as the third ligand is bound.
Group Members
Haynes, C. L., Armentrout, P. B., Perry, J. K., & III, W. A. G. (1995). Experimental and Theoretical Studies of Co(CH_4)_x^+ with x = 1-4. *J. Phys. Chem.*, *99*(17), 6340-6346. https://doi.org/10.1021/j100017a013