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Les Complexes (η6 -Arène)tricarbonylmanganèse Cationiques : Fonctionnalisation, Dédoublement et Applications en Synthèses Organique et Organométallique

Abstract : The synthesis of keto-substituted (η5-cyclohexadienyl)Mn(CO)3 complexes has been achieved by Stille coupling reaction under carbon monoxide atmosphere or by the sequence lithiation, transmetallation to Mn (II) and electrophilic quench by an acyl chloride. Study of their reactivity and theoretical investigations showed that conjugation’s strength is dependant to the position of the keto group on the cyclohexadienyl ring. The development of the synthesis of (η6-bromoarene)Mn(CO)3+ complexes and of the bromide-lithium exchange reaction followed by an electrophilic quench allowed the funtionalization scope of thoses complexes to broaden, allowing for example the formation of complexes substituted on the meta position of an ortho-directing group, on extremity of the cyclohexadiényl ring or of stable bimetallic iron-manganese carbocations. At last, the first general resolution of (η6-arene)Mn(CO)3+ complexes has been developed. Based on the intrinsic electrophilic nature of those cationic complexes, no function in particular is needed and it relies on the addition of a derivative of (D)-(+)-camphor, a cheap natural compound. The conservation of the chiral information has been checked at every stage by radiocrystallographic studies and by 2H NMR in chiral oriented solvent. The preparation of many η5 and η6 enantiopure complexes has been realized and their applications in organic as well as organometallic syntheses studied.
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Antoine Eloi. Les Complexes (η6 -Arène)tricarbonylmanganèse Cationiques : Fonctionnalisation, Dédoublement et Applications en Synthèses Organique et Organométallique. Chimie. Université Pierre et Marie Curie, 2010. Français. ⟨tel-02490853⟩

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