2008
DOI: 10.1021/ja077538q
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Synthesis, Characterization, and Reactivity of a Uranyl β-Diketiminate Complex

Abstract: Addition of 1 equiv of Li(Ar2nacnac) (Ar2nacnac = (2,6-(i)Pr2C6H3)NC(Me)CHC(Me)N(2,6-(i)Pr2C6H3)) to an Et2O suspension of UO2Cl2(THF)3 generates the uranyl dimer [UO2(Ar2nacnac)Cl]2 (1) in good yield. A second species can be isolated in low yield from the reaction mixtures of 1, namely [Li(OEt2)2][UO2(Ar2nacnac)Cl2] (2). The structures of both 1 and 2 have been confirmed by X-ray crystallography. Complex 1 reacts with Ph3PO to generate UO2(Ar2nacnac)Cl(Ph3PO) (3). In addition, 1 reacts with AgOTf and either 1… Show more

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Cited by 101 publications
(99 citation statements)
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“…[27,29] To prevent the formation of polynuclear intermediates leading to disproportionation ours and other groups have designed bulky polydentate ligands or macrocyclic ligands that have resulted in the preparation of stable complexes of pentavalent uranyl. [21,[31][32][33][34] These initial results seemed to validate the general assumption that the formation of cation-cation complexes would inevitably result in the disproportionation of the pentavalent uranyl species.…”
Section: Introductionmentioning
confidence: 53%
“…[27,29] To prevent the formation of polynuclear intermediates leading to disproportionation ours and other groups have designed bulky polydentate ligands or macrocyclic ligands that have resulted in the preparation of stable complexes of pentavalent uranyl. [21,[31][32][33][34] These initial results seemed to validate the general assumption that the formation of cation-cation complexes would inevitably result in the disproportionation of the pentavalent uranyl species.…”
Section: Introductionmentioning
confidence: 53%
“…[1] Cation-cation interactions are known to be important in neptunyl(V) structural chemistry, [13] but are more rarely found in uranyl(VI) compounds because of the lower basicity of the UO 2 2+ oxygen atoms. Dimeric compounds formed through the mutual binding of pentavalent uranyl(V) ions have been proposed as intermediates in the disproportionation of pentavalent uranyl ions to UO 2 2+ and U IV species.[14]As a result, bulky ligands have been used in the past few years to disfavor cation-cation interactions and allow the synthesis of rare UO 2 + complexes, [15][16][17][18][19][20][21] which have been the subject of two recent reviews.[ [8] The presence of antiferromagnetic coupling between the oxo-bridged uranium centers was unambiguously demonstrated for the dimetallic complex but is less evident for the tetrametallic complex. [8] The decomposition of these polymetallic complexes of pentavalent uranyl ions to UO 2 2+ and U IV species starts rapidly after dissolution in organic solvents and is accelerated by traces of water.…”
mentioning
confidence: 99%
“…Dimeric compounds formed through the mutual binding of pentavalent uranyl(V) ions have been proposed as intermediates in the disproportionation of pentavalent uranyl ions to UO 2 2+ and U IV species. [14] As a result, bulky ligands have been used in the past few years to disfavor cation-cation interactions and allow the synthesis of rare UO 2 + complexes, [15][16][17][18][19][20][21] which have been the subject of two recent reviews. [21] In some of the reported UO [8] The presence of antiferromagnetic coupling between the oxo-bridged uranium centers was unambiguously demonstrated for the dimetallic complex but is less evident for the tetrametallic complex.…”
mentioning
confidence: 99%