Serveur d'exploration sur le cobalt au Maghreb

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Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters

Identifieur interne : 000332 ( Istex/Curation ); précédent : 000331; suivant : 000333

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters

Auteurs : Mustapha Bencharif [Algérie] ; Olivier Cador [France] ; Hélène Cattey [France] ; Alexander Ebner [Allemagne] ; Jean-François Halet [France] ; Samia Kahlal [France] ; Walter Meier [Allemagne] ; Yves Mugnier [France] ; Jean-Yves Saillard [France] ; Patrick Schwarz [Allemagne] ; Fatima Zohra Trodi [Algérie, France] ; Joachim Wachter [Allemagne] ; Manfred Zabel [Allemagne]

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RBID : ISTEX:A3880727306C37B2B0BB6632BAD51CE31A841019

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English descriptors

Abstract

Extended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]–/[3]2–/[3]3–/[3]4–/[3]5– regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]– containing salts form with PPh3AuCl or dppe decomposition products like [(PPh3)2Au][CoCl3PPh3] or [Co(CO)2dppe]2(μ‐Te). A neutral cluster comprising the Co@Co8(μ4‐Te)6 core formed in the reaction of [Cp*2Nb(CO)2][Co11Te7(CO)10] with PPh3AuCl, which gave [Co9Te6(CO)4(PPh3)4] (4) after oxidative cluster degradation and CO substitution. 4 was characterized by X‐ray crystallography. DFT calculations carried out on all members of the [3]n (n = +1 to –5) family and on related species indicate that there is no significant Jahn–Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][3] show that the ground state of [3]– is a spin triplet with spins interacting antiferromagnetically in a 1D space.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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DOI: 10.1002/ejic.200701350

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<div type="abstract">Extended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]–/[3]2–/[3]3–/[3]4–/[3]5– regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]– containing salts form with PPh3AuCl or dppe decomposition products like [(PPh3)2Au][CoCl3PPh3] or [Co(CO)2dppe]2(μ‐Te). A neutral cluster comprising the Co@Co8(μ4‐Te)6 core formed in the reaction of [Cp*2Nb(CO)2][Co11Te7(CO)10] with PPh3AuCl, which gave [Co9Te6(CO)4(PPh3)4] (4) after oxidative cluster degradation and CO substitution. 4 was characterized by X‐ray crystallography. DFT calculations carried out on all members of the [3]n (n = +1 to –5) family and on related species indicate that there is no significant Jahn–Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][3] show that the ground state of [3]– is a spin triplet with spins interacting antiferromagnetically in a 1D space.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</div>
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