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

Platinum(IV);Ruthenium(II);C-H Activation;pyrazolyl alkanes

Gurkin, Joshua Taylor ; T. Brent Gunnoe, Committee Chair,Reza A. Ghiladi, Committee Member,Elon A. Ison, Committee Member,Maria T. Oliver-Hoyo, Committee Member,Gurkin, Joshua Taylor ; T. Brent Gunnoe ; Committee Chair ; Reza A. Ghiladi ; Committee Member ; Elon A. Ison ; Committee Member ; Maria T. Oliver-Hoyo ; Committee Member

University:North Carolina State University

关键词: Platinum(IV);    Ruthenium(II);    C-H Activation;    pyrazolyl alkanes;   

Others  :  https://repository.lib.ncsu.edu/bitstream/handle/1840.16/2205/etd.pdf?sequence=1&isAllowed=y

美国|英语

来源: null

【 摘 要 】

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)(PPh₃)(NCMe)][Cl], [EpRu(py)₂Cl][Cl], [EpRu(py)₂Cl][Cl], [EpRu(OHMe)(PMe3)(Cl)][BAr’₄] are reported {Ep = 1,1,1-tris(pyrazolyl)ethane, py = N-pyridine, Ar’ = 3,5-(CF₃)-C₆H₃}.The lack of solubility yielded these complexes ineffective for further synthetic manipulation.Additionally presented is the synthesis and characterization of (tbpy)Pt(Me)₂(I)₂ and (tbpy)Pt(Me)(NHPh)(I)₂ (tbpy = 4,4’-tert-butyl-2,2’-bipyridine).Attempted syntheses of (tbpy)Pt(NHPh)₂(I)₂ and (tbpy)Pt(Cl)(NHPh)(I)₂ are also reported.Initial reactivity of (tbpy)Pt(Me)₂(I)₂ and the decomposition of (tbpy)Pt(Me)(NHPh)(I)₂ are further reported.