Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 NAd (Ad = adamantyl).
Spencer P HeinsPeter T WolczanskiThomas R CundariSamantha N MacMillanPublished in: Chemical science (2017)
Application of the diamide, diimine {-CHN(1,2-C6H4)N(2,6-iPr2-C6H3)}2m ((dadi) m ) ligand to titanium provided adducts (dadi)TiL x (1-L x ; L x = THF, PMe2Ph, (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)TiX (2 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 AdN3 + CO to AdNCO + N2. Kinetics measurements support carbonylation of 2 NAd as the rate determining step. Structural and computational evidence for the observed RNI is provided.