University of Illinois Urbana-Champaign

Synthesis and Characterization of I. Organometallic Amidophenolate Complexes II. Cyanometallate Frameworks

Boyer, Julie L.

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Description

Title
Synthesis and Characterization of I. Organometallic Amidophenolate Complexes II. Cyanometallate Frameworks
Author(s)
Boyer, Julie L.
Issue Date
2008
Doctoral Committee Chair(s)
Rauchfuss, Thomas B.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Language
eng
Abstract
Lastly, the reactivity of organometallic complexes with non-innocent ligands (NIL) was examined. Treatment of PtCl2(diene) with the deprotonated catecholate or amidophenolate ligands afforded the corresponding Pt(NIL)(diene) complexes. The complexes Pt(tBAFPh)(COD), Pt(tBAFPh)(nbd), and Pt(O2C 6H2tBu2)(COD) (H2tBA FPh = 2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol) were examined by cyclic voltammetry. The complexes with amidophenolate ligands displayed milder redox potentials than their catecholate analogues. Treatment of Pt(tBAFPh)(COD) or Pt(tBA FPh)(nbd) with AgPF6 afforded the imino-semiquinones [Pt( tBAFPh)(COD)]PF6 or [Pt(tBA FPh)(nbd)]PF6, respectively. The effect of redox poise of the NIL on the reactivity of the alkene ligand was investigated. The complex [Pt(tBAFPh)(COD)] was unreactive toward nucleophiles, the oxidized derivative [Pt(tBAFPh)(COD)]PF 6, however, rapidly and stereospecifically added alkoxides at the carbon trans to the phenolate. The complexes Pt(tBAFPh)(COD), [Pt(tBAFPh)(COD)]PF6, and Pt( tBAFPh)(C8H12OMe) were crystallographically characterized.
Graduation Semester
2008
Type of Resource
text
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http://hdl.handle.net/2142/84301

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