Synthesis, Structure, and Reactivity of Five-coordinate Platinum(IV) Complexes PDF Download
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Author: Avery T. Luedtke
Publisher:
ISBN:
Category : Platinum compounds
Languages : en
Pages : 151
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Author: Avery T. Luedtke
Publisher:
ISBN:
Category : Platinum compounds
Languages : en
Pages : 151
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Author: Allan J. Canty
Publisher: Springer Science & Business Media
ISBN: 3642174280
Category : Science
Languages : en
Pages : 195
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Book Description
Kyle A. Grice, Margaret L. Scheuermann and Karen I. Goldberg: Five-Coordinate Platinum(IV) Complexes.- Jay A. Labinger and John E. Bercaw: The Role of Higher Oxidation State Species in Platinum-Mediated C-H Bond Activation and Functionalization.- Joy M. Racowski and Melanie S. Sanford: Carbon-Heteroatom Bond-Forming Reductive Elimination from Palladium(IV) Complexes.- Helena C. Malinakova: Palladium(IV) Complexes as Intermediates in Catalytic and Stoichiometric Cascade Sequences Providing Complex Carbocycles and Heterocycles.- Allan J. Canty and Manab Sharma: h1-Alkynyl Chemistry for the Higher Oxidation States of Palladium and Platinum.- David C. Powers and Tobias Ritter: Palladium(III) in Synthesis and Catalysis.- Marc-Etienne Moret: Organometallic Platinum(II) and Palladium(II) Complexes as Donor Ligands for Lewis-Acidic d10 and s2 Centers.
Author: Georgina Giannikopoulos
Publisher:
ISBN:
Category : Ligands (Biochemistry)
Languages : en
Pages : 236
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Author: Deepak Ravindranathan
Publisher:
ISBN:
Category : Chemical bonds
Languages : en
Pages : 88
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The synthesis, structure, and photophysical properties of a series of novel, highly luminescent tridentate platinum complexes with general coordination geometry of (C^N*N)-PtL are reported, where "C^N" denotes a coordination of C and N to the platinum to form a five-membered metallacycle and "N*N" denotes a coordination of two N atoms to the platinum to form a six-membered metallacycle; L is a mono anionic ligand such as halides or acetylides. Compared to the known (C^N^N)-PtL type of complexes that were reported to emit with low quantum yields, the structural modification leads to dramatic improvements in phosphorescence efficiency. For example, new complexes (C^N*N)-PtL with L = hexylacetylide and phenylacetylide emitted intensely with quantum yields of 47% and 56%, respectively, latter of which is among the highest quantum yields reported so far for cyclometalated platinum (II) complexes. Selectivity in C-H bond activation by platinum and the exact mechanism of cycloplatination are issues that still remain unclear. A series of ligands which include sp2/sp3, primary/secondary sp3 C-H bonds, and aromatic/vinylic sp2 C-H bonds with a carbon linker between the bipyridine and the carbon groups have been prepared. All ligands have been attempted for cycloplatination in glacial acetic acid and acetonitrile. All ligands produced the same sp2 C-H bond activated complex in both solvents, which suggests that the linker atom does play a role on selectivity.
Author: Dileep Atchyuth Kumar Vezzu
Publisher:
ISBN:
Category : Platinum compounds
Languages : en
Pages : 291
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The synthesis, structure, and photophysical properties of luminescent platinum (II) complexes with different coordination patterns, (C^C*N^N), (N^C*N), (N^N*C) and (N^N^C) are reported, where "C^N or N^N" denotes a bidentate coordination to the platinum to form a five-membered metallacycle and "C*N" denotes a bidentate coordination to the platinum to form a six-membered metallacycle. Sixteen cyclometalated platinum complexes have been synthesized with different coordination patterns, which include six complexes with tridentate N^C*N cyclometalating ligands (13, 14, 15, 16, 17, and 18), five complexes with N^N*C cyclometalating ligands (19a, 19b, 20a, 20b, and 24), three complexes with N^N^C cyclometalating ligands (21a, 21b, and 29) and two complexes with tetradentate C^C*N^N cyclometalating ligands (33 and 34). The structures of the platinum complexes 13, 15, 16, 18, 19a, 19b, 20a, 21a, 21b, 24, 29, 33, and 39 were determined by single crystal X-ray diffraction. In platinum complexes with five-six membered metallacycle (15, 16, 18, 19a, 19b, 20a, 24, and 39), the square geometry of the complexes is improved when compared to that of platinum complexes with five-five membered metallacycle as the biting angle is increased. The tetradentate coordination (C^C*N^N), square planar geometry of complex 33 are revealed from its X-ray crystal structure. The DFT calculations have been carried out on complexes 13, 14, 15, 16, 17, 18, 33, and 34 to examine the molecular orbital character of the complexes, which are used in interpreting the electronic spectra of the complexes. The photophysical properties of the platinum complexes were studied and a majority of the complexes were highly emissive in solution at room temperature. Complex 13 exhibited the highest quantum yield (65%) among all of the complexes. Self quenching was not observed in a majority of the platinum complexes at lower concentrations. The cytotoxicity (IC50) of the complexes in three lung cancerous cell lines and one prostate cancer cell line were determined by MTT assay. The toxic platinum complexes induced the cell death by triggering apoptosis. The interactions of the platinum complexes with plasmid and calf thymus DNA were studied. Activation of caspase -7, PARP, and p53 were also observed in RV1 and HCC827 cell lines when treated with platinum complexes. Complexes 35, 37 and 38 were more potent than the clinically approved drug, cis-platin.
Author: Stephen Fallis
Publisher:
ISBN:
Category : Cations
Languages : en
Pages : 252
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Book Description
![Synthesis, Structure and Reactivity of Ti(IV) and Ti(II) Complexes Supported by Proximally Bridged P-t-BUTYLCALIX[4]ARENE Ligands PDF](https://books.google.com/books/content/images/frontcover/0XwJtwAACAAJ?fife=w80-h100)
Author: Oleg Viktorovich Ozerov
Publisher:
ISBN:
Category :
Languages : en
Pages : 644
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Author:
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Examples of late transition metal complexes with amido, alkoxo and sulfido ligands are relatively rare in part due to enhanced reactivity based on nucleophilicity and basicity of the heteroatomic ligand (X). The highly nucleophilic and basic character of formally anionic X ligands coordinated to metal centers with low oxidation states is attributable to the disruption of ligand-to-metal pi-bonding. Examples of common reactivity for these systems include nucleophilic addition reactions, insertions of unsaturated substrates, acid/base chemistry with acidic C-H bonds and C-H activation reactions with aromatic substrates. In addition to fundamental reactivity studies, these complexes also offer opportunities for incorporation into catalytic processes. Late transition metal complexes with non-dative X ligands have been implicated in several C-X bond forming reactions and have been demonstrated to activate non-polar substrates. Thus, in order to advance the understanding of these reactive systems and to exploit the prospects for synthetic applications toward small molecule transformations, further study is warranted. Presented herein is the study of (IPr)Cu(NR2), (IPr)Cu(OR) and (IPr)Cu(SR) {IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene} complexes in the catalytic hydroamination of electron-deficient olefins toward regioselective formation of C-N, C-O and C-S bonds. The substrate scope encompasses alkyl and aryl amines, including primary and secondary variants, as well as alcohols and thiols. Olefins with cyano, acyl, and ester functionalities and vinylarenes are reactive. In a demonstration of potential application, the hydroamination of p-nitrostyrene with N-methylbenzylamine by (IPr)Cu(NHPh) provides a straight-forward single-step route to an anti-arrhythmic agent. Mechanistic studies are consistent with a reaction pathway that involves intermolecular nucleophilic addition of the Cu-amido to free olefin. In an effort to obtain more active catalyst systems that.
Author: William Junior Knebel
Publisher:
ISBN:
Category :
Languages : en
Pages : 446
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Author: Terence James Maguire
Publisher:
ISBN:
Category : Coordination compounds
Languages : en
Pages : 300
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Book Description
This thesis describes the synthesis and reactivity of platinum(II) and platinum(IV) complexes with mixed donor ligands containing [P, N, C] and [P, N, O] donor sets derived from iminophosphines and phosphinoamides. Chapter 1 introduces the concepts and principles, like hemilability, that influence the formation of stable complexes and how this stabilisation can influence the reactivity of the complex. This is highlighted using aminophosphines and iminophosphines as examples. In order to present the application of these mixed-donor complexes, a comprehensive overview of platinum complex chemistry, including Pt(IV) complexes, trans complexes and cyclometallates, in medicine is given. Chapter 2 reports the coordination chemistry of two types of [P, N, C] donor ligands; iminophosphines HL1-4 and phosphinoamides HL5-7 to generate a novel library of monodentate, bidentate and tridentate cyclometallated Pt(II) species by a variety of methods. Chapter 3 describes the synthesis of novel ionic, monophosphine substituted Pt(II) complexes of [P, N, C] and [P, N, O] ligands. The iminophosphine ([P, N, C] and [P, N, O]) complexes underwent substitution with all three of the phosphines introduced. However, the success of the reaction of the iminolphosphine [P, N, C] complexes depended on the nature of the phosphine used. This leads to the conclusion that substitution reactions of iminolphosphine complexes are influenced by a combination of basicity and steric bulk of the incoming ligand. Chapter 4 reports the oxidation of bidentate and cyclometallated Pt(II) complexes to generate a novel series of Pt(IV) species. Additionally it reports 1H and 31P{1H} NMR investigations into the reduction of Pt(IV) by low molecular weight thiols and finally describes the reaction of the Pt(II) cyclometallates with the same low molecular weight thiols. All compounds synthesised in chapters 2-4 were characterised by elemental analysis, IR, 1H and 31P{1H} NMR spectoscopies. Selected complexes were also analysed using single X-ray crystal analyses and mass spectrometry.
