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

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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Boyer, Julie L.

Contributors dc:contributor

• Rauchfuss, Thomas B.

• Chemistry, Inorganic

Language dc:language

eng

Identifier

(MiAaPQ)AAI3337704

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84301