Leistungsstarkes Fluoralkoxy‐Molybdän(V)‐Reagens für die selektive oxidative Arenkupplung

Wir stellen ein neues Fluoralkoxy-Molybdan(V)-Reagens 1, mit im Vergleich zu MoCl5 oder MoCl5/TiCl4 hoherer Reaktivitat und Selektivitat in der oxidativen Kupplung von Arenen vor. Haufige Nebenreaktionen wie Chlorierung und/oder Oligomerenbildung werden erheblich reduziert, sodass ein leistungsstarkes und nutzliches Reagens fur die oxidative Kupplung erhalten wird. Theoretische Untersuchungen der Wechselwirkung des Reagens mit 1,2-Dimethoxybenzol-artigen Substraten deuten auf einen Innenspharen-Elektronentransfer gefolgt von einem radikalkationischen Reaktionspfad fur den oxidativen Kupplungsprozess hin. ESR-spektroskopische und elektrochemische Untersuchungen, Rontgenkristallstrukturanalysen, computerchemische Studien sowie vergleichende Substratuntersuchungen ergeben ein hoch konsistentes Bild. Die Substitution von Chlorido- durch Hexafluorisopropoxido-Liganden scheint sowohl die Reaktivitat als auch die Selektivitat des Metallzentrums zu erhohen, weswegen diese Strategie auf andere Metallzentren ubertragbar sein sollte.

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