Actinide alkoxide chemistry

Sluys, William G. Van Der; Sattelberger, Alfred P.

doi:10.1021/cr00104a005

Cited by 85 publications

(44 citation statements)

References 30 publications

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“…In addition, an inductive effect due to the alkyl substituents might increase the strength of the interaction between UO 2 and the alkoxide species generated after proton transfer and thus be a driving force for the elimination of the neutral acid during CID. The preference for formation of alkoxide species would be consistent with previously reported tendencies for lanthanide and actinide species to form alkoxide complexes,12–14 and calculations suggest that replacing OH bonds with OCH 3 within a uranyl complex increases the binding energy to the uranyl ion 6. Our hypothesis was that the composite influence of increased acidity and electron donation by the alkoxides would manifest itself in an increased tendency to eliminate HCl, HBr, HI or HClO 4 at early CID stages (MS/MS and MS 3 ) particularly when compared to CID of the complexes containing H 2 O ligands.…”

Section: Resultssupporting

confidence: 90%

Production and collision‐induced dissociation of gas‐phase, water‐ and alcohol‐coordinated uranyl complexes containing halide or perchlorate anions

Anbalagan

Chien

Gresham

et al. 2004

Rapid Comm Mass Spectrometry

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Electrospray ionization was used to generate mono‐positive gas‐phase complexes of the general formula [UO2A(S)n]+ where A = OH, Cl, Br, I or ClO4, S = H2O, CH3OH or CH3CH2OH, and n = 1–3. The multiple‐stage dissociation pathways of the complexes were then studied using ion‐trap mass spectrometry. For H2O‐coordinated cations, the dissociation reactions observed included the elimination of H2O ligands and the loss of HA (where A = Cl, Br or I). Only for the Br and ClO4 versions did collision‐induced dissociation (CID) of the hydrated species generate the bare, uranyl–anion complexes. CID of the chloride and iodide versions led instead to the production of uranyl hydroxide and hydrated UO. Replacement of H2O ligands by alcohol increased the tendency to eliminate HA, consistent with the higher intrinsic acidity of the alcohols compared to water and potentially stronger UO2O interactions within the alkoxide complexes compared to the hydroxide version. Copyright © 2004 John Wiley & Sons, Ltd.

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Section: Resultssupporting

confidence: 90%

Production and collision‐induced dissociation of gas‐phase, water‐ and alcohol‐coordinated uranyl complexes containing halide or perchlorate anions

Anbalagan

Chien

Gresham

et al. 2004

Rapid Comm Mass Spectrometry

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“…2) was described [41]. Further work by Sen, with use of OCBu t 3 [42], Lappert (also with OCBu t 3 ) [43], and the groups of Clark [44], Deacon [45], and Sattelberger [46] (arylox- 3 which has three coordinate, virtually planar, scandium [41]. ide) has greatly expanded the knowledge of these and related crowded species.…”

Section: Bulky Alkoxide and Aryloxide Ligandsmentioning

confidence: 99%

“…ide) has greatly expanded the knowledge of these and related crowded species. The pre-1990 work on actinide alkoxide chemistry has been summarized in a review [46]. A prominent example of the use of the bulky aryloxide ligand (OC 6 H 3 -2,6-Pr i 2 ) was in the stabilization of the homoleptic dimer {U(OC 6 H 3 -2,6-Pr i 2 ) 3 } 2 ( Fig.…”

Section: Bulky Alkoxide and Aryloxide Ligandsmentioning

confidence: 99%

Some highlights from the development and use of bulky monodentate ligands

Power

2004

Journal of Organometallic Chemistry

149

130

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“…Nach den Anfängen der Entwicklung auf diesem Gebiet in den 1960er und 1970er Jahren8, 11 sind in den letzten drei Jahrzehnten eine Reihe ausgezeichneter Übersichtsartikel erschienen 12–32. Da bereits viele Bereiche (z.…”

Section: Introductionunclassified

Die Renaissance der nichtwässrigen Uranchemie

Liddle

2015

Angewandte Chemie

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Bis zum Jahr 2000 umfasste die nichtwässrige Uranchemie hauptsächlich Metallocen‐ und klassische Alkyl‐, Amid‐ oder Alkoxidverbindungen sowie bekannte Carben‐, Imido‐ und Oxoderivate. Seither hat das Gebiet einen starken Aufschwung erfahren, einhergehend mit der Entwicklung von Hilfsliganden, mehrfach bindenden Ligandenarten, der Aktivierung niedermolekularer Verbindungen und der Untersuchung magnetischer Eigenschaften. Dieser Aufsatz führt in die theoretischen Grundlagen des Gebiets ein, behandelt wichtige Ausgangsstoffe und untersucht neuere Ligandenklassen für Uran, einschließlich Alkyle, Aryle, Arene, Carbene, Amide, Imide, Nitride, Alkoxide, Aryloxide und Oxoeinheiten. Des Weiteren werden die Fortschritte auf dem Gebiet des Einzelmolekülmagnetismus beschrieben, bevor eine Zusammenfassung der Koordination und Aktivierung niedermolekularer Verbindungen, einschließlich Kohlenmonoxid, Kohlendioxid, Stickstoffmonoxid, Distickstoff, weißem Phosphor und Alkanen, gegeben wird.

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Actinide alkoxide chemistry

Cited by 85 publications

References 30 publications

Production and collision‐induced dissociation of gas‐phase, water‐ and alcohol‐coordinated uranyl complexes containing halide or perchlorate anions

Production and collision‐induced dissociation of gas‐phase, water‐ and alcohol‐coordinated uranyl complexes containing halide or perchlorate anions

Some highlights from the development and use of bulky monodentate ligands

Die Renaissance der nichtwässrigen Uranchemie

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