25 research outputs found

    Gastvrijheid en caritas op de grens van Amersfoort en Leusden : de geschiedenis van het Aldegonde Gasthuis 1890-1905

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    De geschiedenis van Huize Aldegonde aan de Arnhemseweg dat in 1889 werd gebouwd als Kinderziekenhuis en in 1890 door baron van Boetzelaer in gebruik gegeven aan de gemeente als gast- en verpleeghuis voor minder bedeelden. In 1907 werd het Aldegonde-Ziekenhuis weer gesloten en een jaar later geschonken aan de toen pas opgerichte Hervormde Vereniging Kinderzorg Utrecht. In 1976 sloot Aldegonde haar poorten en het pand werd gesloopt in 1980

    Het chirurgijnsgilde van Amersfoort

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    Wantin

    Synthesis and characteristic chemistry of sixteen-electron group 6 hydrocarbyl-containing nitrosyl complexes

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    This thesis addresses the non-generality of the previous method used to prepare CpW(NO)(alkyl)2 complexes from their diiodide precursors. The three most significant problems inherent to the original synthetic method were: (a) the reagents being used (i.e. transition-metal dihalide, alkylating agent and solvent), (b) excessive hydrolysis during workup, and (c) thermal decomposition. This work presents a rationalization for, and utilization of, a new general methodology for the preparation of Cp'M(NO)R2 [Cp' = Cp (i5-05H5), Cp* (i5-05Me5); M = Mo, W; R = alkyl, aryl] complexes. Reactions of Cp*M(NO)C12 with (ary1)2Mg‱X(dioxane) [aryl = Ph, p-tolyl, o-tolyl] in THE provide Cp*M(NO)(aryl)2 complexes. These 16-electron diaryl complexes irreversibly form 1:1metal-centered adducts with PMe3. CpW(NO)(o-tolyl)2 is the only isolable diaryl complex of this type that does not incorporate a Cp* ligand. Electrochemical and IR studies indicate that the sediaryl complexes are more potent Lewis acids than their Cp'M(NO)(alkyl)2 congeners. X-raycrystallographic analyses indicate that these diaryl complexes have more sterically accessible metal centers than related dialkyl complexes. The thermal stability of Cp'M (NO)R2 complexes is Cp* >Cp, W > Mo and alkyl > aryl. The relative Lewis acidities of this family of nitrosyl complexes mirrors the thermal stability trend. Reactions of Cp*Mo(NO)C12 with (alky1)2Mg‱X(dioxane) [alkyl = CH2CMe3, CH2CMe2Ph,CH2SiMe3] in THE provide previously inaccessible Cp*Mo(NO)(alkyl)C! and Cp*Mo(N0)(alky1)2 complexes in a stepwise fashion. Cp*Mo(NO)(alkyl)Cl species are comparable in Lewis acidity to related Cp*Mo(N0)(ary1)2 complexes. Cp*Mo(NO)(CH2CMe3)Cl reacts with PMe3 and pyridine to afford metal-centered 18-electronadducts while CO and CNCMe3 readily insert into its Mo-neopentyl bond. The chloride ligand inCp*Mo(NO)(CH2CMe3)Cl is easily abstracted by Ag+ in NCMe to form[Cp*Mo(NO)(CH2CMe3)(NCMe)]BF4. The phosphine complex, Cp*Mo(N0)(CH2CMe3)(PMe3)C1, is readily dehydrohalogenated by LDA in THE to afford the novel cyclometallated dialkyl complex (15,111-05Me4CH2)Mo(N0)(CH2CMe3)(PMe3). Reactions of Cp*Mo(NO)R2 complexes with water afford bimetallic complexes of the type,[Cp*Mo(NO)R]2-(11-0), and free hydrocarbon. A kinetic analysis of the reaction between H2Oand Cp*Mo(N0)(CH2SiMe3)2 implicates Cp*Mo(NO)(CH2SiMe3)(OH) as a key intermediate in the formation of [Cp*Mo(N0)(CH2SiMe3)]2-(A-0). Cp'W(NO)(alkyl)2 complexes are hydrolytically stable, whereas Cp'W(NO)(aryl)2 complexes react vigorously with water providing Cp'W(0)2(aryl) complexes. CpMo(NO)(CH2CMe3)2 thermally decomposes via a first-order intramolecular extrusion of neopentane yielding the 16-electron alkylidene complex, CpMo(NO)(=CHCMe3). A mechanistic analysis of the above-mentioned thermal reaction shows little solvent dependence and suggests a highly ordered transition state. CpMo(NO)(=CHCMe3) cannot be isolated, but it can be trapped with phosphines or pyridine (L) yielding CpMo(NO)(=CHCMe3)L complexes. Primary amines and alcohols add their heteroatom-hydrogen bonds across the Mo=C double bond of CpMo(NO)(=CHCMe3) stereoselectively to give alkyl amide and alkyl alkoxide complexes. CpMo(NO)(=CHCMe3) reacts with CpMo(NO)(CH2CMe3)2 to give [CpMo(NO)](12-11 1:112-N0)(A-CHCMe3)[CpMo(=CHCMe3)], which contains the first g-111:12-nitrosyl ligand.Science, Faculty ofChemistry, Department ofGraduat

    In de regio moet het gebeuren. Naar slagkrachtiger arbeidsmarktbeleid

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