title: Nitrene Insertion into C-C and C-H Bonds of Diamide Diimine Ligands Ligated to Chromium and Iron.
abstract: 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 d(4) 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.
authors.affiliation: Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14850 (USA).
authors.forename: Spencer P
authors.initials: SP
authors.lastname: Heins
authors.affiliation: Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14850 (USA).
authors.forename: Wesley D
authors.initials: WD
authors.lastname: Morris
authors.affiliation: Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14850 (USA). ptw2@cornell.edu.
authors.forename: Peter T
authors.initials: PT
authors.lastname: Wolczanski
authors.affiliation: Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14850 (USA).
authors.forename: Emil B
authors.initials: EB
authors.lastname: Lobkovsky
authors.affiliation: Department of Chemistry, Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas, Box 305070, Denton, TX 76203-5070 (USA). Thomas.Cundari@unt.edu.
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Cundari
keywords: chelates; chromium; iron; nitrene; redox chemistry