Journal of Physical Chemistry, Vol.100, No.21, 8786-8790, 1996
Theoretical and Experimental Studies on the Bond-Dissociation Energies of Al(Methane)(+), Al(Acetylene)(+), Al(Ethene)(+), and Al(Ethane)(+)
The structures and bond dissociation energies (BDEs) for Al(methane)(+), Al(acetylene)(+), Al(ethene)(+), and Al(ethane)(+) have been determined by using both Fourier-transform ion Cyclotron resonance (FTICR) mass spectrometry and the ab initio post-HF methods MP2, MP4, and QCISD(T) with split valence basis sets plus polarization and diffuse functions, i.e., 6-31G(d,p), 6-311+G(d,p), and 6-311+G(3df,2p). The ab initio results indicate the following 300 K data : BDE(Al+-methane) = 5.2, BDE(Al+-acetylene) = 13.2, BDE(Al+-ethene) = 13.6, BDE(Al+-ethane) = 8.4, (end-on), and BPE(Al+-ethane) = 8.5 kcal/mol (side-on). According to the results of the FTICR experiments, the Al+-ligand BDE values increase in the following order : Al+-CH4 < Al+-C2H6 < Al+-C2H4 < Al+-C2H2.
Keywords:COLLISION-INDUCED DISSOCIATION;LIGAND-BINDING-ENERGIES;TRANSITION-METAL ATOMS;GAS-PHASE;ORGANIC-MOLECULES;2-LIGAND COMPLEXES;GAUSSIAN-2 THEORY;POSITIVE-IONS;ORGANOMETALLIC CHEMISTRY;MASS-SPECTROMETRY