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Synthesis of organophosphores complexes of di -and trivalent lanthanides and their application in catalysis.

Abstract : Organo! lanthani de chemistry has long been dominated by cyclopentadienyl-based ligands whereas phosphorus-containing ligands have attracted interest only recently. In this work we show the influence of organophosphorus ligands on the synthesis and reactivity of organolanthanide compounds in three different areas. The first part is dedicated to the synthesis of "new" divalent organolanthanide complexes using both cyclopentadienyl and phospholyl based ligands. A new synthetic method - the reductive approach - is developed which allows the synthesis of base-free divalent thulocenes and unprecedented divalent dysprosium and neodymium ate-complexes. Small molecule activation with these new divalent compounds reveals their strong reducing nature and some differences between cyclopentadienyl- and phospholyl-containing complexes. The second part describes the synthesis of the first trivalent monophospholyl-bis(o-dimethylaminobenzyl)lanthanide complexes by classical salt-metathesis! reactions. In addition, a stable 1H phosphole is used for the first time in a
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Florian Jaroschik. Synthesis of organophosphores complexes of di -and trivalent lanthanides and their application in catalysis.. Chemical Sciences. Ecole Polytechnique X, 2007. English. ⟨pastel-00003025⟩

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