Article

This research focuses on CO2 activation through palladium-carbon bond insertion reactions utilizing (PCP)PdMe and (PCP)PdCH2CHCH2 complexes. These complexes have been effective in catalyzing the carboxylation of ZnMe2 and Bu3SnCH2CHCH2.

A kinetic analysis indicates that CO2 insertion reactions are first order concerning both the metal complex and CO2. The palladium-allyl bond insertion occurs more rapidly, likely through a distinct mechanism that involves a cyclic transition state rather than a traditional insertion.

Additionally, CO2 insertions in palladium hydroxide and hydride yield carbonato and formato complexes, respectively, completing within minutes. The study also includes the reaction of (PCP)PdH with phenylacetylene, producing (PCP)PdCCC6H5 through s-bond metathesis. Crystal structures of the synthesized complexes demonstrate unique packing arrangements influenced by hydrogen bonding.