Chimie de coordination du phosphore aux métaux du groupe 11 : progrès en catalyse de couplage C-N au Cu(I) et nouveaux complexes polyphosphines de l'Au(I)

Nowadays, sustainable development encourages chemists to develop new economic and ecologic synthesis, because natural ressources are reducing. Most exploited ressources are gas and petroleum, but precious metals are also essential. This thesis is focusing on the enhancement of gold and copper complexes, obtained in our laboratory from phosphorous-based ligands. In the first part, we will develop a new system for the N-arylation of pyrazoles from a copper complexe coordinated by a new hybrid phosphinoalkene ligand. In the second part, coordination properties of gold to different ferrocenic polyphosphine will be studied. Several new innovative complexes will be isolated, and could be used in future catalytic or luminescent studies.De nos jours et depuis quelques années maintenant, le principe de développement durable encourage les chimistes de tous horizons à développer de nouvelles méthodes de synthèse économiques et écologiques, les ressources naturelles de notre planète ne sont pas illimitées. Parmi les ressources les plus exploitées, nous trouvons le pétrole et le gaz. Outre ces derniers et le gaz, les métaux précieux sont également devenus indispensables.Cette thèse se concentre sur la valorisation de complexes de cuivre et d’or, obtenus à partir de ligands phosphorés synthétisés au sein du laboratoire. Dans un premier temps, nous verrons la mise au point d’une réaction de N-arylation de pyrazoles catalysée par un complexe de cuivre portant un ligand hybride phosphinoalcène. Dans un deuxième temps, les propriétés de coordination de l’or à différentes polyphosphines ferrocéniques seront étudiées. Plusieurs complexes innovants seront mis en évidence et pourront être utilisés dans le cadre de futures études de catalyse, ou de luminescence

Phosphorous coordination chemistry to group 11 metals : improvements in C-N cross-coupling catalyzed by Cu(I) and new polyphosphinic complexes of Au(I)

De nos jours et depuis quelques années maintenant, le principe de développement durable encourage les chimistes de tous horizons à développer de nouvelles méthodes de synthèse économiques et écologiques, les ressources naturelles de notre planète ne sont pas illimitées. Parmi les ressources les plus exploitées, nous trouvons le pétrole et le gaz. Outre ces derniers et le gaz, les métaux précieux sont également devenus indispensables.Cette thèse se concentre sur la valorisation de complexes de cuivre et d’or, obtenus à partir de ligands phosphorés synthétisés au sein du laboratoire. Dans un premier temps, nous verrons la mise au point d’une réaction de N-arylation de pyrazoles catalysée par un complexe de cuivre portant un ligand hybride phosphinoalcène. Dans un deuxième temps, les propriétés de coordination de l’or à différentes polyphosphines ferrocéniques seront étudiées. Plusieurs complexes innovants seront mis en évidence et pourront être utilisés dans le cadre de futures études de catalyse, ou de luminescence.Nowadays, sustainable development encourages chemists to develop new economic and ecologic synthesis, because natural ressources are reducing. Most exploited ressources are gas and petroleum, but precious metals are also essential. This thesis is focusing on the enhancement of gold and copper complexes, obtained in our laboratory from phosphorous-based ligands. In the first part, we will develop a new system for the N-arylation of pyrazoles from a copper complexe coordinated by a new hybrid phosphinoalkene ligand. In the second part, coordination properties of gold to different ferrocenic polyphosphine will be studied. Several new innovative complexes will be isolated, and could be used in future catalytic or luminescent studies

Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment

A smart steric control of the metallocene backbone in bis- and poly­(phosphino)­ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold­(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky <i>tert</i>-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes <i>meso</i>-1,1′-bis­(diphenylphosphino)-3,3′-di-<i>tert</i>-butylferrocene (<b>4-m</b>), <i>rac</i>-1,1′-bis­[bis­(5-methyl-2-furyl)­phosphino]-3,3′-di-<i>tert</i>-butylferrocene (<b>5-r</b>), and <i>rac</i>-1,1′-bis­(diphenylphosphino)-3,3′-bis­[(tri-<i>iso</i>-propylsilyl)­oxy]­ferrocene (<b>6-r</b>) were used to form dinuclear gold complexes. Coordination of <i>tert</i>-butylated ferrocenyl phosphines generated aurophilic interactions in the corresponding dinuclear gold complexes, contrary to gold­(I) complexes reported with 1,1′-bis­(diphenylphosphino)­ferrocene. The structurally related tetraphosphine 1,1′,2,2′-tetrakis­(diphenylphosphino)-4,4′-di-<i>tert</i>-butylferrocene (<b>11</b>) also gave access to mononuclear, dinuclear, and the original trinuclear gold chloride aurophilic complexes in which 14e^– to 16e^– gold centers coexist. In such complexes, nonbonded (“through-space”) ³¹P–³¹P′ nuclear spin couplings were evidenced by high-resolution NMR. In these interactions nuclear spin information is transferred between the lone-pair electron of an uncoordinated phosphorus P and a phosphorus P′ that is involved in a σ covalent bond Au–P′. The dinuclear aurophilic complex displayed a concerted shuttling of its [ClAu···AuCl] fragment between the four phosphorus donors of the tetraphosphine ligand. Thus, an aurophilic Au···Au bond, which is assumed to be a weak energy interaction, can be conserved within a dynamic shuttling process at high temperature involving an intramolecular coordination–decoordination process of digold­(I) at phosphorus atoms

Gold(I) Complexes Nuclearity in Constrained Ferrocenyl Diphosphines: Dramatic Effect in Gold‐Catalyzed Enyne Cycloisomerization

International audienceDi-tert-butylated-bis(phosphino)ferrocene ligands bearing phosphino substituents R (R=phenyl, cyclohexyl, isopropyl, mesityl, or furyl) allow tuning the selective formation of Au(I) halide complexes. Thus, dinuclear linear twocoordinate, but also rare mononuclear trigonal three-coordinate and tetrahedral four-coordinate complexes were formed upon tuning of the conditions. Both Au(I) chloride and rarer Au(I) iodide complexes were synthesized, and their X-ray diffraction analysis are reported. The significance of the control of structure and nuclearity in Au(I) complexes is further illustrated herein by its strong effect on the efficiency and selectivity of gold-catalysed cycloisomerization. Cationic linear digold(I) bis(dicyclohexylphosphino) ferrocenes outperform other catalysts in the demanding regioselective cycloisomerization of enyne sulphonamides into cyclohexadienes. Conversely, tetrahedral and trigonal cationic monogold(I) complexes were found incompetent for enyne cycloaddition. We used the two-coordinate linear electron-rich Au(I) complex 2b (R=Cy) to extend the scope of selective intramolecular cycloaddition of different 1,6-enyne sulfonylamines with high activity and excellent selectivity to the endo cyclohexadiene products

First Annelated Azaphosphole-Ferrocenes: Synthetic Pathways and Structures

The first annelated bis- and mono-3<i>H</i>-1,3-azaphosphole ferrocene sandwich compounds have been synthesized from aminoferrocenes, and their X-ray structures are compared to those of their selenide-protected PSe analogues, showing net discrepancies both in metallocene backbone conformation and in fused-ring planarity

First Annelated Azaphosphole-Ferrocenes: Synthetic Pathways and Structures

The first annelated bis- and mono-3<i>H</i>-1,3-azaphosphole ferrocene sandwich compounds have been synthesized from aminoferrocenes, and their X-ray structures are compared to those of their selenide-protected PSe analogues, showing net discrepancies both in metallocene backbone conformation and in fused-ring planarity

(Cycloheptadienyl)diphenylphosphine: A Versatile Hybrid Ligand

(3,5-Cycloheptadienyl)­diphenylphosphine is easily synthesized from the reaction of diphenylphosphine with 1,3,5-cycloheptatriene. This new phosphine-diene has been coordinated as a monodentate P ligand with Pt, Pd, Au, Ni, and Ru; as a bidentate (P, olefin) ligand with Pt and Pd; and as a tridentate (P, diene) ligand with Rh. Fluxional properties of several complexes have been studied via NMR experiments and theoretical consideration