Synthesis AndRreactivity of Copper(I), Copper(II), Platinum(II) and Platinum(IV) Complexes with Non-dative Heteroatomic Ligands

Synthesis AndRreactivity of Copper(I), Copper(II), Platinum(II) and Platinum(IV) Complexes with Non-dative Heteroatomic Ligands
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Download or read book Synthesis AndRreactivity of Copper(I), Copper(II), Platinum(II) and Platinum(IV) Complexes with Non-dative Heteroatomic Ligands written by and published by . This book was released on 2004 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Synthesis AndRreactivity of Copper(I), Copper(II), Platinum(II) and Platinum(IV) Complexes with Non-dative Heteroatomic Ligands Related Books

Synthesis AndRreactivity of Copper(I), Copper(II), Platinum(II) and Platinum(IV) Complexes with Non-dative Heteroatomic Ligands
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Type: BOOK - Published: 2004 - Publisher:

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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 nucleophilici
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Keywords: hydroamination, copper(I), platinum(IV), platinum(II), hydroalkoxylation, hydrothiolation, C-H activation.
Synthesis and Reactivity of Copper Complexes Possessing Non-dative Ligands
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Presented herein are the isolation and characterization of a number of new copper(I) halide complexes and the first two examples of monomeric copper(I) amido co