Complex 4 coordinates with system-generated CO, replacing a PI ligand to form complex 8. This coordination facilitates CO insertion into the Ti-C bond, yielding the unique titanium α-ketocarboxylate complex 9. The four-membered Ti-O-C-C titanaoxetane ring structure, previously observed 9 in rhodium, silver, and other metals, appears for the first time in titanium chemistry as a ketocarboxylate ring.