Synthesis, Characterization, and Reactivity of New 16-electron Platinum(II) Propargyl Complexes PDF Download
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Author: David Glenn Schimpff
Publisher:
ISBN:
Category :
Languages : en
Pages : 244
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Author: David Glenn Schimpff
Publisher:
ISBN:
Category :
Languages : en
Pages : 244
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Author: Ruslan S. Pryadun
Publisher:
ISBN:
Category :
Languages : en
Pages : 154
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Author: César M. Lozano Paulino
Publisher:
ISBN:
Category : Complex compounds
Languages : en
Pages : 222
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Author: Claudio Pio Mastrocinque
Publisher:
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Category : Chemistry, Inorganic
Languages : en
Pages : 0
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Author: Julienne Sarabia
Publisher:
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Category : Ligands
Languages : en
Pages : 0
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Author: Jun Wen
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 96
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Author:
Publisher:
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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: Monique Doyon
Publisher:
ISBN:
Category :
Languages : en
Pages : 356
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"New platinum(II) complexes of the type (Pt(A$ sp prime$)Cl$ sb3 rbrack sp-$, Pt(A)(A$ sp prime$)Cl$ sb2$ and Pt(A)(A$ sp prime$)I$ sb2$, where A = methylamine, ethylamine, cyclobutylamine and cyclopentylamine and A$ sp prime$ = 1-adamantanamine, 2-adamantanamine and 1-methyladamantanamine have been synthesized. The structure of (2-adamH) (Pt(EtNH$ sb2$)Cl$ sb3$) complex has been determined by X-ray diffraction." --
Author: American Chemical Society. Committee on Professional Training
Publisher:
ISBN: 9780841227231
Category : Science
Languages : en
Pages : 1700
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Author:
Publisher:
ISBN:
Category :
Languages : en
Pages :
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A series of square planar platinum(II) complexes with the mer-coordinating tridentate ligand, pip & sub2;NCN & sup-; (pip & sub2;NCNH = 1,3?bis(piperdylmethyl) benzene) has been synthesized. The lowest emissive excited states of these complexes can be tuned by varying the properties of the monodentate ligand. Colorless halide complexes and the pyridine adduct exhibit weak red emissions originating from a lowest triplet ligand field (3LF) excited state. In contrast, yellow-green emissions from Pt(pip & sub2;NCN)(4-phenylpyridine))+; originate from a lowest 3TT?TT* state. Similarly, (Pt(pip & sub2;NCN))2(mƯL)2+; dimers exhibit emission from a lowest 3LF excited state (L=1,2-bis(4-pyridyl)ethane), a lowest 3TT-TT* excited state (L=trans-1,2-bis(4-pyridyl)ethylene or 4,4'-bipyridine) or a lowest triplet metal-to-ligand charge-transfer excited state (L=pyrazine), depending on the bridging ligand. A series of platinum(II) terpyridyl complexes with aryl ligands has been synthesized. The complexes undergo two one-electron reduction processes near -0.9 and -1.4 V vs. Ag/AgCl. In the cyclic voltammograms of complexes unsubstituted at the 2 and 6 positions of the aryl ligand, the first reduction exhibits larger (>59 mV) differences between the anodic and cathodic peak potentials than observed for complexes with methyl groups at the 2 and 6 positions. The accumulated data are consistent with the formation of dimers that reduce at different potentials than the monomers, causing the first reduction wave to appear broadened. Protection of the axial sites of the metal center appears to interfere with dimerization. 77 K glassy solution emission measurements confirm that steric effects can be utilized to control intermolecular metalʺʺʺmetal and ligandʺʺʺligand stacking interactions in solutions of these complexes. The first examples of platinum complexes that undergo reversible and cooperative thermal two-electron transfer have been prepared. The tpy ligand of Pt(tpy)(pip & sub2;NCN))+; is tridentate and the pip & sub2;NCN & sup-; ligand is monodentate, bonded through the central aryl group. Cyclic voltammograms of this complex exhibit two reversible oneƯelectron tpy-centered reductions and a nearly reversible two-electron platinum-centered oxidation at ""0.40 V vs. Ag/AgCl. Electrochemical studies of a series of model complexes establish that both potentially tridentate ligands are required for reversible two-electron transfer. A detailed analysis leads to the suggestion that the ligands preorganize around the platinum(II) center, resulting in a 5- or 6-coordinate electrochemically active species.
