Synthesis, Reactivity, and Characterization of Ruthenium Complexes Containing a Single Bipyridine Ligand PDF Download
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Author: Simon I. Barsoum
Publisher:
ISBN:
Category : Bipyridine
Languages : en
Pages : 142
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Author: Simon I. Barsoum
Publisher:
ISBN:
Category : Bipyridine
Languages : en
Pages : 142
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Author: Ryan Mahabir
Publisher:
ISBN:
Category :
Languages : en
Pages : 200
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Author: Xinwei Yang
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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Since the discovery of nonlinear effects, both the theory and measurement techniques have been developed significantly, especially since the invention of the laser. However, structure-NLO property relationships for organometallics as well as their NLO mechanisms are far less explored than those of organic molecules and inorganic salts. The greater flexibility and exceptionally large NLO responses of organometallic compounds attracts chemists to this field. Modification of coordinated co-ligands in organometallic systems has influence on the NLO merit by introducing new electronic charge-transfer transitions, oxidation state and coordination sphere of the metal centers. In this work, the donor sets of the ruthenium complexes were modified from the most investigated (P-P)(P-P) to (N-N)(P-P) and (N-P)2 and a series of ruthenium complexes were synthesized and characterized. In Chapter 2, the study of the Ru(N-N)(P-P) complexes is detailed. Three bidentate diphosphine ligands (dppe, dppb and dppf) and one diimine ligand (tert-Bu-bpy) were selected for this study as the diphosphine and diimine ligands, respectively. Ruthenium halide and mono-alkynyl complexes were obtained successfully. Their optical, electrochemical and spectroelectrochemical properties were examined and are discussed. The formation of eta3- and eta1-butenynyl complexes was confirmed by single-crystal X-ray diffraction. Attempts towards bis-alkynyl complexes were made, but no conclusive evidence could be obtained to confirm the successful synthesis of this species. In Chapter 3, the focus of the work is the study of ruthenium complexes with a (N-P)2 donor set. Two iminophosphine ligands, 2-(diphenylphosphino)pyridine (PPh2py) and 8-(diphenylphosphino)quinoline (PPh2qn), were selected for this study. The cis-RuCl2(N-P) complexes and the corresponding dimers were synthesized and characterized. Their optical and electrochemical properties were measured and are discussed. In Chapter 4, the quadratic and cubic nonlinear optical properties of organometallic complexes were explored by hyper-Rayleigh scattering (HRS) and frequency-depentdent Z-scan techniques, respectively. The first hyperpolarizabilities of the ruthenium halide and mono-alkynyl complexes described in Chapter 2 were determined by HRS measurements. The second hyperpolarizabilities of some organometallic complexes synthesized by the Humphrey group and the collaborators were measured by the Z-scan technique.
Author: Lisa Frances Szczepura
Publisher:
ISBN:
Category :
Languages : en
Pages : 310
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Author:
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Category :
Languages : en
Pages :
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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 â'Ơ-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)][BArÃØâ'Ơâ"Ø4] are reported {Ep = 1,1,1-tris(pyrazolyl)ethane, py = N-pyridine, ArÃØâ'Ơâ"Ø = 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 = 4,4ÃØâ'Ơâ"Ø-tert-butyl-2,2ÃØâ'Ơâ"Ø-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 re.
Author: Ivan Stibor
Publisher: Springer
ISBN: 9783642445187
Category : Science
Languages : en
Pages : 0
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with contributions by numerous experts
Author: Carol A. Bessel
Publisher:
ISBN:
Category :
Languages : en
Pages : 314
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Author: Ajay Kumar Mishra
Publisher: CRC Press
ISBN: 1351616498
Category : Science
Languages : en
Pages : 260
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This book will describe Ruthenium complexes as chemotherapeutic agent specifically at tumor site. It has been the most challenging task in the area of cancer therapy. Nanoparticles are now emerging as the most effective alternative to traditional chemotherapeutic approach. Nanoparticles have been shown to be useful in this respect. However, in view of organ system complicacies, instead of using nanoparticles as a delivery tool, it will be more appropriate to synthesize a drug of nanoparticle size that can use blood transport mechanism to reach the tumor site and regress cancer. Due to less toxicity and effective bio-distribution, ruthenium (Ru) complexes are of much current interest. Additionally, lumiscent Ru-complexes can be synthesized in nanoparticle size and can be directly traced at tissue level. The book will contain the synthesis, characterization, and applications of various Ruthenium complexes as chemotherapeutic agents. The book will also cover the introduction to chemotherapy, classification of Ru- complexes with respect to their oxidation states and geometry, Ruthenium complexes of nano size: shape and binding- selectivity, binding of ruthenium complexes with DNA, DNA cleavage studies and cytotoxicity. The present book will be more beneficial to researchers, scientists and biomedical. Current book will empower specially to younger generation to create a new world of ruthenium chemistry in material science as well as in medicines. This book will be also beneficial to national/international research laboratories, and academia with interest in the area of coordination chemistry more especially to the Ruthenium compounds and its applications.
Author: Youxiang Wang
Publisher:
ISBN:
Category :
Languages : en
Pages : 416
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Author: Michał Pawel Łomzik
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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The main goal of this thesis was synthesis and preliminary characterization of novel ruthenium(II) polypyridyl complexes bearing biologically active molecules as potential theranostic agents. Luminescence for the diagnostic applications, and cytotoxicity for the anticancer, therapeutic applications are considered as the theranostic properties. Four new ligands containing biologically active moieties - 5-(4-4'-methyl-[2,2'-bipyridine]-4-ylbut-1-yn-1-yl)pyridine-2-carbaldehyde semicarbazone (L1), 3-(5-4'-methyl-[2,2'-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L2), 5,5-dimethyl-3-(5-4'-methyl-[2,2'-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L3) and [1-(5-4'-methyl-[2,2'-bipyridine]-4-ylpentyl)-2,5-dioxoimidazolidin-4-yl]urea (L4) were synthesized and characterized. The ligands were used to obtain nine novel ruthenium(II) polypyridyl complexes. Six complexes were synthesized with ligand L1 ([Ru(bpy)2(L1)]2+, [Ru(Mebpy)2(L1)]2+, [Ru(tBubpy)2(L1)]2+, [Ru(Phbpy)2(L1)]2+, [Ru(dip)2(L1)]2+, [Ru(SO3dip)2(L1)]2-) and three with ligands L2, L3 and L4 ([Ru(bpy)2(L2)]2+, [Ru(bpy)2(L3)]2+, [Ru(bpy)2(L4)]2+) (bpy = 2,2'-bipyridine, Mebpy = 4,4'-dimethyl-2,2-bipyridine, tBubpy = 4,4'-tert-butyl-2,2'-bipyridine, Phbpy = 4,4'-diphenyl-2,2-bipyridine, dip = 4,7-diphenyl-1,10-phenantroline and SO3dip = 4,7-di-(4-sulfonatophenyl)-1,10-phenantroline). The spectroscopic and photophysical properties of those complexes were determined. The presence of ligands L1-L4 in the structure of the complex decreased luminescence quantum yield and luminescence lifetime in comparison with unmodified [Ru(bpy)3]2+ complex. The theoretical calculations have shown that ligands L1-L4 do not have influence on ruthenium core geometry. However, they increased the energy of the HOMO that resulted in a shorter band gap. The simulated electronic absorption spectra were in a good agreement with the experimental data. The interactions between the studied ruthenium complexes and human serum albumin (HSA) were investigated. All studied Ru(II) complexes exhibited strong affinity to HSA with the association constant 105 M-1s-1, which suggests formation of Ru complex-HSA adducts. It was also determined that ruthenium complexes most likely bind to the hydrophobic pocket of protein, located in Sudlow's site I in the subdomain II A. Preliminary cytotoxicity evaluation for the studied ruthenium complexes showed their cytotoxic activity towards cancer cell lines. Those results, together with good luminescence properties of the studied ruthenium complexes (luminescence lifetimes and luminescence quantum yield) make them interesting candidates for potential theranostic applications.
