Stereoselectivity and nonmigratory insertion mechanism of dimethylacetylene dicarboxylate into metallocene‐hydride of Cp₂M(L)H [Cp =η⁵‐C₅H₅; M = Nb, V; L = CO, P (OMe)₃]: A DFT study

Abstract

The insertion of an alkyne into transition metal–hydrogen bonds is a key elementary step in catalytic polymerization and hydrogenation processes. It was found that a (Z)‐ or (E)‐type alkyenyl complex can be formed through trans/cis stereospecific processes. In this work, the reaction mechanism of Cp2M(L)H [Cp = η5‐C5H5; M = Nb, V; L = CO, P (OMe)3] with dimethylacetylene dicarboxylate (DMAD), and the factors influencing the stereoselectivity have been investigated based on density functional theory calculations. The calculated results show that all of the reactions are exothermic. For L = CO, the Z‐isomer product forms first even at low temperatures because of the low Gibbs free energy barrier (ΔG#). Then the Z‐pro converts to E‐pro, while for L = P (OMe)3, the exclusive product is the E‐isomer. For different metal centers, the reaction mechanisms of the Cp2M(CO)H + DMAD (M = Nb and V) reaction are similar, while their products are different at room temperature. For M = Nb, because the energy barrier of the isomerization from Z‐pro to E‐pro is low and the relative free energies of Z‐pro and E‐pro are almost equal, both Z‐pro and E‐pro can be obtained. While for the Cp2V(CO)H + DMAD reaction, only the Z‐pro can be obtained under mild conditions, E‐pro can be obtained only at high temperatures. For the Cp2M(CO)H+DMAD(M=V and Nb) reactions, the formation of E‐isomer products proceeds via two five‐membered ring transition states. The calculated results provide an reasonable explanation for the experimental results and predict a new insertion reaction.