Theoretical study of the reaction of titanium ion with ethane — Structure, mechanism, and potential energy surface

Abstract

Density functional theory in its B3LYP variant has been used to study the reaction of Ti + ( 4 F) with ethane in the gas phase. The potential energy surface corresponding to [Ti, C 2 , H 6 ] + , has been examined in detail at the B3LYP/6-311++G(3df,3pd)//B3LYP/6-311+G(d,p) level of theory. The quality of this theoretical method has been calibrated against the available thermochemical data. Three activation branches, C-H, C-C, and synchronous C-H and C-C bond activations, were proposed along the reaction coordinates, and two new mechanisms, the sequential 1,1-H 2 elimination and the concerted elimination of CH 4 , were found.

Vibrational Spectroscopy and Structural Analysis of V+(C2H6)n Clusters (n = 1–4)

“…The C–C bond length is calculated to change by negligible amounts for all isomers, but the vibrational frequency associated with the C–C stretch decreases by 2.5% for only the side-on isomer. This indicates that the side-on isomer may have greater potential for C–C bond activation, which is generally in line with the mechanisms proposed for metal-initiated C–C bond cleavage in a number of systems. ,,,, …”

“…This indicates that the side-on isomer may have greater potential for C−C bond activation, which is generally in line with the mechanisms proposed for metal-initiated C−C bond cleavage in a number of systems. 1,10,24,51,57 ■ CONCLUSIONS Photodissociation spectroscopy of vanadium cation−ethane clusters in the C−H stretching region in concert with computational results provides information about cluster binding motifs. Clusters exhibit a general tendency to bind in a square-planar geometry about vanadium when possible.…”