title: "Oxidative addition" to a Zirconium(IV) redox-active ligand complex.
abstract: A strategy to enable reactivity analogous to oxidative addition is presented for d(0) transition-metal complexes. The reaction of the redox-active ligand 2,4-di-tert-butyl-6-tert-butylamidophenolate (ap) with ZrCl(4)(THF)(2) affords the new complex Zr(IV)(ap)(2)(THF)(2). This compound is formally zirconium(IV) and contains no d electrons; however, exposure of Zr(IV)(ap)(2)(THF)(2) to chlorine gas results in swift chlorine addition at the zirconium metal center via one-electron oxidation of each ap ligand. The diradical product, Zr(IV)Cl(2)(isq)(2) (isq = 2,4-di-tert-butyl-6-tert-butyliminosemiquinone), has been characterized by X-ray crystallography, electron paramagnetic resonance spectroscopy, and SQUID magnetometery.
authors.affiliation: Department of Chemistry, University of California, Irvine, 92697, USA.
authors.forename: Karen J
authors.initials: KJ
authors.lastname: Blackmore
authors.forename: Joseph W
authors.initials: JW
authors.lastname: Ziller
authors.forename: Alan F
authors.initials: AF
authors.lastname: Heyduk