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

Inorganic Chemistry
Julie L BoyerScott R Wilson

Abstract

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

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Citations

Jul 13, 2011·Inorganic Chemistry·Wolfgang Kaim
Jun 28, 2013·Inorganic Chemistry·Olayinka A Olatunji-Ojo, Thomas R Cundari
Sep 25, 2014·Chemistry : a European Journal·Naina DeibelBiprajit Sarkar
Aug 8, 2018·Chemistry : a European Journal·Jarl Ivar van der Vlugt
Aug 18, 2010·Angewandte Chemie·Dan A SmithPhilip W Dyer
Jul 26, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·C Daniel VarnadoChristopher W Bielawski
Mar 26, 2014·Chemistry : a European Journal·Alexa ParetzkiWolfgang Kaim
Nov 23, 2017·Journal of the American Chemical Society·Lukasz MendeckiKatherine A Mirica

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