In the context of converting CO2 into valuable products, transition metal complexes are promising tools to perturb its electronic structure for activation. A good way to enter into catalytic cycles is the reductive homocoupling of CO2 to form oxalate. Our research has focused on utilizing titanium tris-anilide complexes to stabilize doubly reduced carbon dioxide for reaction with small molecules. Presented here is the synthesis of the bridging CO22- complex [(Ti(N[t-Bu]Ar)3)2(�2-CO2-?2O,C:?1O')] (1  , Ar = 3,5-Me2C6H3) and its straightforward conversion into the symmetric oxalate complex [(Ti(N[t-Bu]Ar)3)2(�2-C2O4-?1O:?1O')] (2  ) by exposure to an atmosphere of CO2. 1   features the unprecedented �2-?2O,C:?1O'  bonding mode for CO2. Characterization data for 1  will be discussed particularly with regard to the fluxional coordination behavior of the central carbon atom to both metal centers, possibly via a �2-?1O:?1O'-dioxacarbene as transition state.

Formation of oxalate by reaction of CO2 with doubly reduced CO2 fixed between titanium tris-anilide complexes

246th National Meeting (2013)

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