Comparative Reactivity of Zr– and Pd–Alkyl Complexes with Carbon Dioxide

Structure/reactivity trends and DFT studies reveal mechanistic differences and parallels for the carboxylation of Zr and Pd alkyls. CO2 reacts with Cp2ZrMe(C6D5Cl)+ >104 faster than with Cp2ZrMe2, yielding monoacetate products in both cases. These reactions proceed by insertion mechanisms in which Zr- - -O interactions activate the CO2. In contrast, CO2 reacts readily with [(PO-iPr)PdMe2]− (PO-iPr– = 2-PiPr2-4-Me-C6H3SO3 –) to yield [(PO-iPr)PdMe(OAc)]− but not with (PO-iPr)PdMe(L) species. Carboxylation of [(PO-iPr)PdMe2]− occurs by direct SE2 attack of CO2 at the Pd–Me trans‑to‑P group, and the nucleophilicity of the Pd–Me group controls the reactivity. However, the SE2 process is accelerated by a Li+- - -OCO interaction when Li+ is present.