Redox activation of alkene ligands in platinum complexes with non-innocent ligands


The reactivity of metal olefin complexes with non-innocent ligands (NILs) was examined. Treatment of PtCI 2(diene) with the deprotonated catechol or aminophenol ligands afforded the corresponding Pt(NIL)(diene) complexes. The Pt( tBA FPh)(COD), R( tBA FPh)(nbd), and Pt(O 2C 6H 2tBu 2)(COD) (H 2tBA FPh = 2-(2-trifluoromethyl)anilino-4,6-di-tertbutylphenol, H 2O 2C 6H 2tBu 2 = 3,5-di-ferf-butylcatechol) complexes were examined by cyclic voltammetry. Treatment of P t(BA fPh)(COD) or Pt( tBA fPh)(nbd) with AgPF 6 afforded the imino-semiquinones [Pt( tBA FPh)(COD)]PF 6 or [Pt( tBA FPh)(nbd)]PF 6, respectively. The [Pt( tBA FPh)(COD)] complex was unreactive toward nucleophiles, whereas the oxidized derivative, [Pt( tBA FPh)(COD)]PF 6, rapidly and stereospecifically added alkoxides at the carbon trans to the phenolate. The Pt( tBA FPh)(COD), [Pt( tBA FPh)(COD)]PF 6, Pt( tBA FPh)(C 8H 12OMe), and [Cp 2Co][Pt-( tBA FPh)(C 8H 12OMe)] complexes were characterized crystallographically. © 2009 American Chemical Society.

Publication Title

Inorganic Chemistry