Date: December 19, 2009
Creator: Boyer, Julie L.; Cundari, Thomas R., 1964-; DeYonker, Nathan J.; Rauchfuss, Thomas B. & Wilson, Scott R.
Description: This article discusses redox activation of alkene ligands. The reactivity of metal olefin complexes with non-innocent ligands (NILs) was examined. Treatment of PtCl2(diene) with the deprotonated catechol or aminophenol ligands afforded the corresponding Pt(NIL)(diene) complexes. The Pt(ͭBAfPh)(COD), Pt(tBAfPh)(nbd), and Pt(O2C6H2tBu2)(COD) (H2tBAfPh = 2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol, H2O2C6H2tBu2 = 3,5-di-tert-butylcatechol) complexes were examined by cyclic voltammetry. Treatment of Pt(tBAfPh)(COD) or Pt(tBAfPh)(ndb) with AgPF6 afforded the imino-semiquinones [Pt(tBAfPh)(COD)] PF6 or [Pt(tBAfPh)(nbd)]PF6 respectively. The [Pt(tBAfPh)(COD)] complex was unreactive toward nucleophiles, whereas the oxidized derivative, [Pt(tBAfPh)(COD)]PF6, rapidly and stereospecifically added alkoxides at the carbon trans to the phenolate. The Pt(tBAfPh)(COD), [Pt(tBAfPh)(COD)]PF6, Pt(tBAfPh)(C8H12OMe), and [Cp2Co][Pt-(tBAfPh)(C8H12OMe)] complexes were characterized crystallographically.
Contributing Partner: UNT College of Arts and Sciences