Search

The impact of redox non-innocence (RNI) on chemical reactivity is a forefront theme in coordination chemistry. A diamide diimine ligand, [{-CH=N(1,2- C6H4)NH(2,6-iPr2C6H3)}2]n (n=0 to -4), (dadi)n, chelates Cr and Fe to give [(dadi)M] ([1Cr(thf)] and [1Fe]). Calculations show [1Cr(thf)] (and [1Cr]) to have a d4 Cr configuration antiferromagnetically coupled to (dadi)2-*, and [1Fe] to be S= 2. Treatment with RN3 provides products where RN is formally inserted into the C-C bond of the diimine or into a C-H bond of the diimine. Calculations on the process support a mechanism in which a transient imide (imidyl) aziridinates the diimine, which subsequently ring opens. [ABSTRACT FROM AUTHOR]

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 - (4 n + 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 - (4 n ). 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., (This journal is © The Royal Society of Chemistry 2017.)