Theoretical Investigation Of Reaction Mechanisms Of Co~+ With The Oxo-organics

Density functional theory (DFT) has been employed to survey the gas-phase reactions of the oxo-organics with Co+. In the reaction of Tetrahydrofuran(THF) with Co+(3F), geometries for all the stationary points involved are fully optimized at the B3LYP/6-311++G(d,p) and the reaction is analyzed in terms of the topology of potential energy surface. Approach of cobalt cations towards the THF molecule results in the O attached encounter isomer. Through the activation of the C-O bond,(1)following by the C?-H and the C?-H shift, (2)active the C-H bond before C?-H and the C?-H shift lead to the loss of H2O while following by the C?-H shift and the nonreactive dissociation of the Co+-C1 bond and C-O bond can lead to the loss of HCHO.The hydride abstraction for producing CoH + C4H7O+ arises from nonreactive dissociation of the CoH-C4H7O+ bond following a charge-transfer step from Co+H-C4H7O. In the reaction of Co+ with propionaldehyde, geometries for all the stationary points involved in the reactions are investigated at the B3LYP/6-311++G(d,p) level while the energies are investigated at the B3LYP/6-311++G(2df,2pd) level. Eight different"classical"O and"nonclassical"ethyl-H attached isomers are found for the Co+- propionaldehyde complexes. The classical complexes are much more stable than the nonclassical ones. Extensive conversions could occur readily between these encounter complexes. All conceivable reaction pathways from each encounter complex to the products observed experimentally are carefully surveyed and the most possible reaction mechanisms are derived. Activation of the C-C bond of propionaldehyde by Co+ through both the classical and nonclassical complexes leads to the loss of C2H6 which can also be get through the aldehyde-H activation. The loss of H2 arises from Co+ insertion into the polar C?-H bond in the classical complexes as well as from aldehyde-H activation. C?-H activation is unlikely be important. According to our research, HCHO is the impossible production. In the reaction of Co+ with propionaldehyde, geometries for all the stationary points involved in the reactions are investigated at the B3LYP/6-311++G (d,p) level while the energies are investigated at the B3LYP/6-311++G (2df,2pd) level. The cobalt cation can easily activated the O=O bond,by the dissociation of the Co-C bond, we can get the production of CH3O+Co+CH3O. Otherwise, by the activation of two ethyl-Hs, the H2 will be producted.The theoretical work sheds new light on the title reactions and can be considered as a new approach to the reaction mechanisms of transition metal ions with the oxo-organics.