Exploring the peri-, chemo-, and regioselectivity of addition of technetium metal oxides of the type TcO3L (L = Cl–, O–, OCH3, CH3) to substituted ketenes: a DFT computational study

Abstract

The addition of TcO3L (L = Cl, O–, OCH3, CH3) to substituted ketenes along various addition pathways was studied with density functional theory calculations to explore the peri-, chemo-, and regioselectivity of the reactions. In the reactions of TcO3L with dimethyl ketene, the results show that for L = O– and CH3, [1 + 1] addition to form a triplet zwitterionic intermediate is the preferred first step; for L = Cl, the [3 + 2]C=C addition across the O–Tc–Cl bond is the preferred first step and for L = OCH3 the [3 + 2]C=C addition across the O–Tc–OCH3 bond is the preferred first step. In the reactions of TcO3Cl with substituted ketenes, [1 + 1] addition to form a triplet zwitterionic intermediate is the preferred first step for X = Ph, CN, and Cl; the [3 + 2]C=C addition across the O–Tc–O bond of the complex is the preferred first step for X = H, while the [3 + 2]C=C addition across the O–Tc–CH3 bond is the preferred first step. Reactions involving a change in the oxidation state of metal have high activation barriers, while reactions that do not involve a change in oxidation state have low activation barriers. Reactions of ketenes with TcO3L complexes have lower activation barriers for the preferred addition pathways than those of the ReO3L complexes reported in the literature. Thus, the TcO3L complexes may be better catalysts for the activation of the C=C bonds of substituted ketenes than the reported ReO3L complexes.