Investigating the Weak to Evaluate the Strong: An Experimental Determination of the Electron Binding Energy of Carborane Anions and the Gas phase Acidity of Carborane Acids
Five CHB11X6Y5- carborane anions from the series X = Br, Cl, I and Y = H, Cl, CH3 were generated by electrospray ionization, and their reactivity with a series of Brønsted acids and electron transfer reagents were examined in the gas phase. The undecachlorocarborane acid, H(CHB11Cl11), was found to be far more acidic than the former record holder, (1-C4F9SO2)2NH (i.e., ΔH°acid = 241 ± 29 vs 291.1 ± 2.2 kcal mol-1) and bridges the gas-phase acidity and basicity scales for the first time. Its conjugate base, CHB11Cl11-, was found by photoelectron spectroscopy to have a remarkably large electron binding energy (6.35 ± 0.02 eV) but the value for the (1-C4F9SO2)2N- anion is even larger (6.5 ± 0.1 eV). Consequently, it is the weak H-(CHB11Cl11) BDE (70.0 kcal mol-1, G3(MP2)) compared to the strong BDE of (1-C4F9SO2)2N-H (127.4 ± 3.2 kcal mol-1) that accounts for the greater acidity of carborane acids.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 971892
- Report Number(s):
- PNNL-SA-70756; JACSAT; KC0301020; TRN: US201004%%343
- Journal Information:
- Journal of the American Chemical Society, Vol. 131, Issue 50; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
Similar Records
Mechanistic and theoretical analysis of the oxidative addition of H{sub 2} to six-coordinate molybdenum and tungsten complexes M(PMe{sub 3}){sub 4}X{sub 2} (M = Mo, W; X = F, Cl, Br, I): An inverse equilibrium isotope effect and an unprecedented halide dependence
Equilibrium Acidities and Homolytic Bond Dissociation Energies of Acidic C H Bonds in Alpha-Arylacetophenones and Related Compounds