Personne : Boudreau, Josée
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Boudreau
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Josée
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Département de chimie, Faculté des sciences et génie, Université Laval
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ncf11861306
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Publication Accès libre Coordination of a bifunctional ligand to a rhodium(III) dimethyl complex : Lewis acidity enhancement by chelation(American Chemical Society, 2007-06-12) Boudreau, Josée; Mathiotte, Sophie; Drouin, Frédéric; Fontaine, Frédéric-Georges; Michaud, Annie; Thibault, Marie-Hélène; Sigouin, OlivierThe addition of the ambiphilic compound (Me2PCH2AlMe2)2 (1) to Cp*RhMe2(DMSO) (DMSO = dimethylsulfoxide) (2) gives Cp*RhMe2(PMe2CH2AlMe2·DMSO) (3·DMSO). The addition of Lewis acids (LA) such as La(dbm)3 (dbm = dibenzoylmethane) and AlMe3 to a solution of complex 3·DMSO gives a competition reaction that results in the formation of LA·DMSO and Cp*RhMe2(PMe2CH2AlMe2) (3). When heated to 40 °C, complex 3 ionizes to a putative zwitterionic species, Cp*Rh+Me(PMe2CH2AlMe3-) (3‘), which is converted to [Cp*Rh(Me)(μ2-η2-Me2PCH2)]2 (4) irreversibly. Spin saturation transfer experiments demonstrated that the rate of the methyl abstraction by the alane moiety was 0.76 ± 0.09 s-1, while the rate of abstraction of the methyl in Cp*RhMe2(PMe3) by AlMe3 was 0.10 ± 0.02 s-1. The zwitterionic species 3‘ could be trapped in solution by addition of PMe3 to afford both Cp*Rh+Me(PMe3)(Me2PCH2AlMe3-) (5) and [Cp*Rh+Me(PMe3)(Me2PCH2AlMe2)]AlMe4- (6). When compound 1 was added to complex 3‘, the formation of the zwitterionic complex Cp*Rh+Me(η2-Me2PCH2Al-Me2CH2PMe2) (7) was observed.Publication Accès libre Coordination of ethylene to a zwitterionic Rh(III) half-sandwich complex : influence of ambiphilic Ligands on reactivity(ACS, 2011-01-18) Boudreau, Josée; Fontaine, Frédéric-GeorgesThe reactivity of Rh(III) half-sandwich complex Cp*RhMe2(κP-μAl-MePMe2CH2AlMe2) 2 (Cp* = η5-pentamethylcyclopentadienyl) with ethylene was investigated. Coordination of ethylene (or ethylene-d4) gave a mixture of products including as principal species zwitterionic complexes Cp*Rh+Me(C2H4)(PMe2CH2AlMe3−) 4 (or 4-d4) and [Cp*Rh+Me(C2H4)(PMe2CH2AlMe3−)][AlMe3] (4′), after the abstraction of a Rh-methyl group by the pendant Lewis acid, and Cp*RhMe2(PMe2CH2AlMe2·C2H4) (5). Heating this reaction mixture at 50 °C results in the generation of propene (or propene-d3,4), methane (or methane-d1), and trace amounts of butene, as organic materials, as well as previously characterized [Cp*RhMe(μ2-η2(P,C)-PMe2CH2)]2 (10) and rhodium(I) species. Two different pathways for the reactivity of the zwitterionic π-complex were investigated by density functional theory (DFT). It is likely that propene is formed by β-hydride elimination from a cationic Rh-propyl fragment that is generated either by insertion of ethylene into a Rh−C bond or by a nucleophilic attack of the methyl-aluminate fragment on coordinated ethylene. After release of propene, the neutral complex Cp*RhHMe(PMe2CH2AlMe2) 11 is most likely responsible for the reductive elimination of methane.Publication Accès libre MS-TOF study of the formation of thiolato bridged rhodium oligomers(Wiley, 2010-04-08) Boudreau, Josée; Grenier-Desbiens, Jérôme; Fontaine, Frédéric-GeorgesThe complex [Cp*Rh(μ‐SPh)3RhCp*]Cl was used as a starting material to synthesize various oligomeric materials of the general formula [Cp*Rh(μ‐SPh)x(μ‐Cl)3–x{Rh(μ‐SPh)3}nRhCp*] (x = 1 to 3; n = 1 to 4), which are formally formed by insertion of nRh(SPh)3 units into one μ‐Rh–SPh bond. The insertion of Ir(SPh)3 was also observed to generate theheterotrimetallic species. All complexes were observed by using HRMS‐TOF and [Cp*Rh(μ‐SPh)3Rh(μ‐SPh)3RhCp*]Cl, [3+]Cl, was characterized by using X‐ray crystallography.