Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti[double bond, length as m-dash]NAd (Ad =
Spencer P Heins1, Peter T Wolczanski1, Thomas R Cundari2
1Cornell University , Dept. Chemistry & Chemical Biology , Baker Laboratory , Ithaca , NY 14853 , USA .
Abstract:
Application of the diamide, diimine {-CH[double bond, length as m-dash]N(1,2-C6H4)N(2,6-iPr2-C6H3)}2 ((dadi) ) ligand to titanium provided adducts (dadi)TiL (1-L ; L = THF, PMe2Ph, (CNMe)2), which possess the redox formulation [(dadi)4-]Ti(iv)L , 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 impedes binding by CO, and permits catalytic conversion of AdN3 + CO to AdNCO + N2. 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.
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