Quantum chemical study of ethylene addition to group-7 oxo complexes MO 2(CH 3)(CH 2) (M = Mn, Tc, Re)

Abstract

Quantum chemical calculations using DFT at the B3LYP level have been carried out for the reaction of ethylene with the group-7 compounds ReO 2(CH 3)(CH 2) ( Re1), TcO 2(CH 3)(CH 2) ( Tc1) and MnO 2(CH 3)(CH 2) ( Mn1). The calculations suggest rather complex scenarios with numerous pathways, where the initial compounds Re1– Mn1 may either engage in cycloaddition reactions or numerous addition reactions with concomitant hydrogen migration. There are also energetically low-lying rearrangements of the starting compounds to isomers which may react with ethylene yielding further products. The [2 + 2] Re,C cycloaddition reaction of the starting molecule Re1 is kinetically and thermodynamically favored over the [3 + 2] C,O and [3 + 2] O,O cycloadditions. However, the reaction which leads to the most stable product takes place with initial rearrangement to the dioxohydridometallacyclopropane isomer Re1a that adds ethylene with concomitant hydrogen migration yielding Re1a- 1. The latter reaction has a slightly higher barrier than the [2 + 2] Re,C cycloaddition reaction. The direct [3 + 2] C,O cycloaddition becomes more favorable than the [2 + 2] M,C reaction for the starting compounds Tc1 and Mn1 of the lighter metals technetium and manganese but the calculations predict that other reactions are kinetically and thermodynamically more favorable than the cycloadditions. The reactions with the lowest activation barriers lead after rearrangement to the ethyl substituted dioxometallacyclopropanes Tc1a- 1 and Mn1a- 1. The manganese compound exhibits an even more complex reaction scenario than the technetium compounds. The thermodynamically most stable final product of ethylene addition to Mn1 is the ethoxy substituted metallacyclopropane Mn1a- 2 which has, however, a high activation barrier.