Synthesis and Characterization of Ruthenium(II) and Platinum(IV) Complexes with Anionic Heteroatomic Ligands

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Title: Synthesis and Characterization of Ruthenium(II) and Platinum(IV) Complexes with Anionic Heteroatomic Ligands
Author: Gurkin, Joshua Taylor
Advisors: T. Brent Gunnoe, Committee Chair
Reza A. Ghiladi, Committee Member
Elon A. Ison, Committee Member
Maria T. Oliver-Hoyo, Committee Member
Abstract: Isolated and fully characterized complexes of late transition metals in low oxidation states possessing amido and alkoxo ligands are relatively rare. These ligands often exhibit nucleophilic and/or basic reactivity. This reactivity is due, at least in part, to the disruption of ligand to metal à €-bonding. Reports of early transition metals with low d-electron counts with imido ligands facilitating C-H activation suggest that if later transition metals with amido or aryloxo ligands can be isolated, C-H activation reactivity may be observed. Ruthenium(II) complexes that catalyze the H/D exchange of N-H and O-H protons at anilido and hydroxo ligands, respectively, with deuterated solvents have been reported, and studies of related systems could shed significant light on C-H activation in these types of reactions. Observing changes in the rate of C-H activation based on specific changes to transition metal complexes could give insight into the creation of highly active C-H activation catalysts. Presented here are synthetic efforts toward late transition metal complexes with formally anionic heteroatomic ligands. The synthesis and initial characterization of [EpRu(Cl)(PPh<sub>3</sub>)(NCMe)][Cl], [EpRu(py)<sub>2</sub>Cl][Cl], [EpRu(py)<sub>2</sub>Cl][Cl], [EpRu(OHMe)(PMe3)(Cl)][BAr’<sub>4</sub>] are reported {Ep = 1,1,1-tris(pyrazolyl)ethane, py = N-pyridine, Ar’ = 3,5-(CF<sub>3</sub>)-C<sub>6</sub>H<sub>3</sub>}. The lack of solubility yielded these complexes ineffective for further synthetic manipulation. Additionally presented is the synthesis and characterization of (tbpy)Pt(Me)<sub>2</sub>(I)<sub>2</sub> and (tbpy)Pt(Me)(NHPh)(I)<sub>2</sub> (tbpy = 4,4’-tert-butyl-2,2’-bipyridine). Attempted syntheses of (tbpy)Pt(NHPh)<sub>2</sub>(I)<sub>2</sub> and (tbpy)Pt(Cl)(NHPh)(I)<sub>2</sub> are also reported. Initial reactivity of (tbpy)Pt(Me)<sub>2</sub>(I)<sub>2</sub> and the decomposition of (tbpy)Pt(Me)(NHPh)(I)<sub>2</sub> are further reported.
Date: 2009-08-13
Degree: MS
Discipline: Chemistry
URI: http://www.lib.ncsu.edu/resolver/1840.16/2205


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