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Phosphinines as Precursors for Phosphabarrelenes and Phosphinine Anions: Coordination Chemistry, Catalysis and Stabilisation of Nanoparticles

Abstract : Phosphinines, the phosphorus analogues of pyridines, are the common basis of the present thesis work here. In the first part, the various synthetic routes for the synthesis of phosphinines their electronic properties and their application in transition metal catalysis are summarized. Bidentate, tridentate and tetradentate ligands could be generated by the nucleophilic attack of organolithium reagents on phosphinines with pending diphenylphosphine groups. The use of monoanionic pincer complex derived from diphenylphosphinomethane ( dppm) was studied with special emphasis on the activation of poorly reactive moieties such as C-H bonds and on the dehydrogenation of borane adducts. The third part of this work, describes the synthesis of 3,5-substituted phosphinines via a desilylation method starting from the corresponding 2,6-(bistrimethylsilyl)phosphinines. The use of these 3,5-substituted phosphinines on the stabilization of metal(O)-transition metal (Au, Ni) nanoparticles was studied. In the last part of this work the use of phosphinines as precursors for the generation of bulky monodentate phosphines, the so called phosphabarrelens was studied. The electronic properties of these scarcely studied ligands was investigated experimentally and by the means of DFT calculations (CDA). The use of these ligands in coordination chemistry has allowed for the isolation of various coordination complexes of phosphabarrelenes with transition metals (Groups 9-11). Interestingly these ligands are sui table for the stabilization of highly unsaturated 14VE Pt(O) and Pd(O) complexes. These complexes could be successfully applied in cross-coupling and hydrosilylation reactions.
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https://pastel.archives-ouvertes.fr/pastel-00005638
Contributor : Ecole Polytechnique <>
Submitted on : Wednesday, January 6, 2010 - 8:00:00 AM
Last modification on : Wednesday, March 20, 2019 - 12:12:32 PM
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Matthias Blug. Phosphinines as Precursors for Phosphabarrelenes and Phosphinine Anions: Coordination Chemistry, Catalysis and Stabilisation of Nanoparticles. Chemical Sciences. Ecole Polytechnique X, 2009. English. ⟨NNT : 2009EPXX0035⟩. ⟨pastel-00005638⟩

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