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The Complex Reduction Chemistry of (abpy)PtCl2, abpy = 2,2''-Azobispyridine: Formation of Cyclic [(.mu.,.eta.2:.eta.1-abpy)PtCl]22+ with a New Coordination Mode for abpy

The result's identifiers

  • Result code in IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F04%3A00107595" target="_blank" >RIV/61388955:_____/04:00107595 - isvavai.cz</a>

  • Result on the web

  • DOI - Digital Object Identifier

Alternative languages

  • Result language

    angličtina

  • Original language name

    The Complex Reduction Chemistry of (abpy)PtCl2, abpy = 2,2''-Azobispyridine: Formation of Cyclic [(.mu.,.eta.2:.eta.1-abpy)PtCl]22+ with a New Coordination Mode for abpy

  • Original language description

    The structurally characterized (abpy)PtCl2, abpy = 2,2''-azobispyridine, reveals a strong metal/ligand T interaction as supported by DFT calculations. Unexpectedly, its chemical or electrochemical reduction occurs irreversibly to yield EPR-detectable {(mu,eta(2):eta(2)-abpy)[PtCl2](2)}(.-) and, as the main product of chloride dissociation, the structurally identified and DFT-calculated dinuclear [(mu,eta(2):eta(1)-abpy)PtCl](2)(2+) with a novel coordination mode for abpy and isolated as tetrachlorozincate. Stepwise reversible one-electron reduction of that dimer, separated by 0.24 V, exhibits an intense near-infrared band for the monocationic intermediate [(abpy(-1))(abpy)Pt2Cl2](.+) at 1220 nm (epsilon = 3370 M-1 cm(-1)) which is attributed to a ligand-to-ligand intervalence charge-transfer transition.

  • Czech name

    Souhrná redukční chemie komplexu (abpy)PtCl2, abpy = 2,2''-azobispyridine: Tvorba cyklického [(.mu.,.eta.2:.eta.1-abpy)PtCl]22+ s novým koordinačním modem u abpy a absorbce

  • Czech description

    Strukturně charakterizovaný (abpy)PtCl2, abpy = 2,2''-azobispyridin vykazuje silnou metal/ligand pi-interakci, jak ověřeno DFT výpočty. Neočekávaně, jeho chemická nebo electrochemická redukce probíhá irreversibilně a poskytuje EPR detekovatelný {(mu,eta(2):eta(2)-abpy)[PtCl2](2)}(.- ) a, jako hlavní produkt disociace chloridu, strukturně identifikovaný a DFT-výpočtem charakterizovaný dvojjaderný [(mu,eta(2):eta(1)-abpy)PtCl](2)(2+) s novým koordinačním modem u abpy, izolovaný jak tetrachlorozinečnatan.Postupné reversibilní jednoelektronové redukce tohoto dimeru jsou oddělené 0.24 V a intermediát [(abpy(-1))(abpy)Pt2Cl2](.+) vykazuje intenzivní NIR pás u 1220 nm (epsilon = 3370 M-1 cm(-1)) který přísluší ligand-ligand intervalenčnímu přenosu náboje.

Classification

  • Type

    J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

  • CEP classification

    CF - Physical chemistry and theoretical chemistry

  • OECD FORD branch

Result continuities

  • Project

    Result was created during the realization of more than one project. More information in the Projects tab.

  • Continuities

    Z - Vyzkumny zamer (s odkazem do CEZ)

Others

  • Publication year

    2004

  • Confidentiality

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Data specific for result type

  • Name of the periodical

    Inorganic Chemistry

  • ISSN

    0020-1669

  • e-ISSN

  • Volume of the periodical

    43

  • Issue of the periodical within the volume

    19

  • Country of publishing house

    US - UNITED STATES

  • Number of pages

    8

  • Pages from-to

    5973-5980

  • UT code for WoS article

  • EID of the result in the Scopus database