Synthesis and investigation of novel two-coordinate 1st row transition metal complexes
Final Report Abstract
The two-coordinate titanium project had significant difficulties, particularly with the stability of the desired products. Reduction of a variety of titanium halide precursors was fruitless. However, we were able to synthesize and characterize the first examples of titanium cAAC complexes in multiple oxidation states. Interestingly, the titanium dichloride supported by two redox-active cAAC ligands features diradicaloid character. Furthermore, it was demonstrated in this work that the (aryl)(silyl)amido could be transformed into (aryl)imido upon a silyl abstraction reaction with cAAC. This indeed provides us a novel synthetic access to titanium imido complexes. Moreover, we reduced a zwitterionic Ti(IV) imido complex bearing a cationic cAAC unit, and were able to isolate and characterize a cAAC ligand-centered neutral silyl radical.
