Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti[double bond, length as m-dash]NAd (Ad = adamantyl)

Application of the diamide, diimine {–CH[double bond, length as m-dash]N(1,2-C(6)H(4))N(2,6-(i)Pr(2)-C(6)H(3))}(2) ( m ) ((dadi)( m )) ligand to titanium provided adducts (dadi)TiL( x ) (1-L( x ); L( x ) = THF, PMe(2)Ph, (CNMe)(2)), which possess the redox formulation [(dadi)(4–)]Ti(iv)L( x ), and 22 πe(–) (4n + 2). Related complexes containing titanium-ligand multiple bonds, (dadi)Ti[double bond, length as m-dash]X (2 [double bond, length as m-dash]X; X = O, NAd), exhibit a different dadi redox state, [(dadi)(2–)]Ti(iv)X, consistent with 20 πe(–) (4n). The Redox Non-Innocence (RNI) displayed by dadi( m ) impedes binding by CO, and permits catalytic conversion of AdN(3) + CO to AdNCO + N(2). Kinetics measurements support carbonylation of 2 [double bond, length as m-dash]NAd as the rate determining step. Structural and computational evidence for the observed RNI is provided.