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Theses

Ligands ambiphiles phosphine-borane : synthèse et coordination

Abstract : In the first chapter, a bibliographic study describes the differing behaviour of the Lewis acids of group 13 in particular boron, in organometallic chemistry. Although often used as a co-activator, when it is attached to an organometallic complex, it can (a) activate an M-X bond by intramolecularly, (b) act as a coordination site to guide a substrate towards the reactive centre or (c) interact directly with the metal.

In the second chapter, the synthesis and study of the structures adopted by the ambiphilic ligands themselves are discussed.

In the third chapter, the coordination of the monophosphane-borane ligands with square planar d8 ML4 complexes is described. Two different coordination modes can be obtained, the first with a “spectator” boron Lewis acid, and the second with a Cl→B intramolecular interaction.

In the fourth chapter, the use of the diphosphane-borane ligands allows the description of a third coordination mode, in which the borane moiety interacts directly with the metal. The characterisation of rhodium, platinum and palladium complexes shows a variation of the strength of the interaction depending on the metal.

Finally, in the fifth chapter, the use of a gold precursor complex and monphosphine-borane ligands of increasing boron Lewis acidity allows the description of an original Au-B interaction.

All the studies were carried out by a combination of experimental and computational methods in collaboration with Karinne Miqueu of the “Université de Pau et des Pays de l'Adour”.
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Submitted on : Monday, November 26, 2007 - 1:59:50 PM
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Sylvain Bontemps. Ligands ambiphiles phosphine-borane : synthèse et coordination. Autre. Université Paul Sabatier - Toulouse III, 2006. Français. ⟨tel-00192021⟩

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