Author: Carrie L. Winker
Publisher:
ISBN:
Category : Transition metals
Languages : en
Pages : 140
Book Description
Synthesis, Characterization, and Reactivity of Binuclear Platinum and Palladium Diphosphine Complexes
Author: Carrie L. Winker
Publisher:
ISBN:
Category : Transition metals
Languages : en
Pages : 140
Book Description
Publisher:
ISBN:
Category : Transition metals
Languages : en
Pages : 140
Book Description
Synthesis, Characterization, and Reactivity of Binuclear Platinum
Author: Chapman McCann Wright
Publisher:
ISBN:
Category : Transition metals
Languages : en
Pages : 100
Book Description
Publisher:
ISBN:
Category : Transition metals
Languages : en
Pages : 100
Book Description
Investigations of the Reactivity of Palladium and Platinum Complexes with Molecular Oxygen and Characterization of a Gold(III)-alkene Complex
Author: Margaret Louise Scheuermann
Publisher:
ISBN:
Category : Gold compounds
Languages : en
Pages : 119
Book Description
Understanding the reactivity of metal complexes with molecular oxygen will facilitate the development of catalysts that can enable the widespread use of molecular oxygen as an oxidant for organic synthesis. This thesis presents two new classes of reactions between metal complexes and molecular oxygen. Neutral five-coordinate Pt complexes were tested for reactivity in the presence of molecular oxygen. In arene solution, the complexes (t̳B̳u̳̳M̳e̳2̳ nacnac)PtMe3 (1, t̳̳B̳u̳M̳e̳2̳ nacnac- = [((4-tBu-2,6-Me2C6H2)NC(CH3))2CH]-), (M̳e̳3̳ Me-nacnac)PtMe3 (2, M̳e̳3̳ Me-nacnac- = [((2,4,6-Me3C6H2)NC(CH3))2CCH3]-), and (t̳B̳u̳2̳ PyPyr)PtMe3 (3, t̳B̳u̳2̳ PyPyr- = 3,5-di-tert-butyl-2-(2-pyridyl)pyrrolide) reacted immediately with oxygen to form peroxo species in which two oxygen atoms bridge between the metal center and a carbon atom in the ligand backbone. In contrast, no reaction between ( i̳P̳r̳2̳ AnIm)PtMe3 (4a, i̳P̳r̳2̳ AnIm− = [o- C66H4-{N(C6H3 i Pr2)}(CH=NC6H3 i Pr2)]−) or (M̳e̳3̳ AnIm)PtMe3 (4b, M̳e̳̳3̳ AnIm− = [o-C6H4- {N(C6H2Me3)}(CH=NC6H2Me3)]−) and oxygen was observed. As activation of oxygen by five- coordinate PtIV species was found to involve cooperation between the metal center and the ligand, the ability of the ligand to participate in the oxygen binding appears to be a vital component. Oxygen atom transfer reactions of the novel peroxo species are also presented. In a separate study, an unusual reaction involving the activation of both molecular oxygen and a C-H bond at the same metal center was investigated. Pd(P(Ar)(tBu)2)2 (15, Ar = naphthyl) was found to react with molecular oxygen at room temperature in arene solvent to form a hydroxide dimer in which one equivalent of phosphine per Pd was lost and the remaining phosphine was cyclometalated through the naphthyl ring. At low temperature, two intermediates were observed. The nature of these intermediates suggests a mechanism involving initial reaction of Pd(P(Ar) (tBu)2)2 with O2 followed by the C-H activation step. In a final chapter unrelated to oxygen reactivity, the generation and characterization of a gold III̳-alkene complex by NMR and X-ray crystallography is presented. Such species have been proposed as intermediates in catalytic reactions but until recently none had been observed.
Publisher:
ISBN:
Category : Gold compounds
Languages : en
Pages : 119
Book Description
Understanding the reactivity of metal complexes with molecular oxygen will facilitate the development of catalysts that can enable the widespread use of molecular oxygen as an oxidant for organic synthesis. This thesis presents two new classes of reactions between metal complexes and molecular oxygen. Neutral five-coordinate Pt complexes were tested for reactivity in the presence of molecular oxygen. In arene solution, the complexes (t̳B̳u̳̳M̳e̳2̳ nacnac)PtMe3 (1, t̳̳B̳u̳M̳e̳2̳ nacnac- = [((4-tBu-2,6-Me2C6H2)NC(CH3))2CH]-), (M̳e̳3̳ Me-nacnac)PtMe3 (2, M̳e̳3̳ Me-nacnac- = [((2,4,6-Me3C6H2)NC(CH3))2CCH3]-), and (t̳B̳u̳2̳ PyPyr)PtMe3 (3, t̳B̳u̳2̳ PyPyr- = 3,5-di-tert-butyl-2-(2-pyridyl)pyrrolide) reacted immediately with oxygen to form peroxo species in which two oxygen atoms bridge between the metal center and a carbon atom in the ligand backbone. In contrast, no reaction between ( i̳P̳r̳2̳ AnIm)PtMe3 (4a, i̳P̳r̳2̳ AnIm− = [o- C66H4-{N(C6H3 i Pr2)}(CH=NC6H3 i Pr2)]−) or (M̳e̳3̳ AnIm)PtMe3 (4b, M̳e̳̳3̳ AnIm− = [o-C6H4- {N(C6H2Me3)}(CH=NC6H2Me3)]−) and oxygen was observed. As activation of oxygen by five- coordinate PtIV species was found to involve cooperation between the metal center and the ligand, the ability of the ligand to participate in the oxygen binding appears to be a vital component. Oxygen atom transfer reactions of the novel peroxo species are also presented. In a separate study, an unusual reaction involving the activation of both molecular oxygen and a C-H bond at the same metal center was investigated. Pd(P(Ar)(tBu)2)2 (15, Ar = naphthyl) was found to react with molecular oxygen at room temperature in arene solvent to form a hydroxide dimer in which one equivalent of phosphine per Pd was lost and the remaining phosphine was cyclometalated through the naphthyl ring. At low temperature, two intermediates were observed. The nature of these intermediates suggests a mechanism involving initial reaction of Pd(P(Ar) (tBu)2)2 with O2 followed by the C-H activation step. In a final chapter unrelated to oxygen reactivity, the generation and characterization of a gold III̳-alkene complex by NMR and X-ray crystallography is presented. Such species have been proposed as intermediates in catalytic reactions but until recently none had been observed.
Synthesis and Characterization of Bimetallic Palladium, and Platinum Complexes Resulting from Chelating Tertiary/secondary Diphosphine Ligands
Author: Carolyn Supplee
Publisher:
ISBN:
Category :
Languages : en
Pages : 276
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 276
Book Description
Toward the Upgrading of Hydrocarbons
Author: Paul Frederick Oblad
Publisher:
ISBN:
Category : Dimers
Languages : en
Pages : 438
Book Description
Publisher:
ISBN:
Category : Dimers
Languages : en
Pages : 438
Book Description
Synthesis, Characterization, and Biological Activity of Hydroxylated Diphosphine Complexes of Ruthenium, Platinum, and Palladium
Author: Ana Clara Zampirolli Leal
Publisher:
ISBN:
Category : Palladium
Languages : en
Pages : 0
Book Description
Publisher:
ISBN:
Category : Palladium
Languages : en
Pages : 0
Book Description
Heterobimetallic Diphosphine Complexes of Nickel, Palladium, and Platinum: Syntheses, Characterization and Reactivity
Author: Michelle Marie Setzer
Publisher:
ISBN:
Category : Reactivity (Chemistry)
Languages : en
Pages : 44
Book Description
Publisher:
ISBN:
Category : Reactivity (Chemistry)
Languages : en
Pages : 44
Book Description
Synthesis and Reactivity of Nickel, Palladium, and Platinum Phosphine Complexes with Hydridoamido, Hydridophenoxo, and Dithiooxalato Ligands
Author: Robert L. Cowan
Publisher:
ISBN:
Category :
Languages : en
Pages : 358
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 358
Book Description
D10 Palladium and Platinum Complexes with Alkene and Diimine Ligands
Author: Janet Lynne Whittemore
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 180
Book Description
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 180
Book Description
Synthesis, Characterization and Redox Studies of Platinum and Palladium Complexes with Mer-coordinating Ligands
Author: Seher Kuyuldar Tastan
Publisher:
ISBN:
Category :
Languages : en
Pages : 206
Book Description
Synthetic, structural, spectroscopic, and redox studies of platinum(II) and palladium(II) compounds with mer-coordinating ligands have been undertaken in an effort to better understand the role of the metal and the ligands in controlling d^6/d^8 electron-transfer reactions. A series of Pd(pip2NCN)X (pip2NCNH=1,3-bis(piperdylmethyl)benzene) and [Pd(pip2NNN)X]X (X=Cl, Br, I) (pip2NNN=2,6- bis(piperdyl-methyl)pyridine) complexes are reported. Electronic spectra are consistent with stabilization of ligand-to-metal-charge-transfer states as the ancillary ligand is varied along the ClBr
Publisher:
ISBN:
Category :
Languages : en
Pages : 206
Book Description
Synthetic, structural, spectroscopic, and redox studies of platinum(II) and palladium(II) compounds with mer-coordinating ligands have been undertaken in an effort to better understand the role of the metal and the ligands in controlling d^6/d^8 electron-transfer reactions. A series of Pd(pip2NCN)X (pip2NCNH=1,3-bis(piperdylmethyl)benzene) and [Pd(pip2NNN)X]X (X=Cl, Br, I) (pip2NNN=2,6- bis(piperdyl-methyl)pyridine) complexes are reported. Electronic spectra are consistent with stabilization of ligand-to-metal-charge-transfer states as the ancillary ligand is varied along the ClBr