Haptotropic rearrangements in heterocycles-MLn complexes. I. [Thiophene-Rh(PH3)(3)](+)

A theoretical analysis of the haptotropic rearrangements involving thiophen e and [Rh(PH3)(3)](+) is presented. This haptotropic rearrangement is invol ved in the C-S bond activation of thiophene by d(8)-ML3 fragments. In this study, two theory levels, the second order Moller-Plesset perturbation theo ry (MP2) and density-functional theory (DFT-B3LYP), are employed. The pathw ay discussed in this paper connects an eta(4) coordination mode with an eta (3) one. The results suggest that for the fragment studied in this work, an eta(3) precursor of the C-S cleavage is preferred over the other one propo sed in the Literature. (C) 1999 Elsevier Science B.V. All rights reserved.