Monocyclooctatetraenyl(dithiolene)uranium Compounds

Arliguie, Thérèse; Thuéry, Pierre; Fourmigué, Marc; Ephritikhine, Michel

doi:10.1002/ejic.200400403

Cited by 19 publications

(21 citation statements)

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“…The dianion [U(C 8 H 8 )(dddt) 2 ] 2− was obtained by treatment of [U(C 8 H 8 )-(BH 4 ) 2 )(THF)] with Na 2 dddt, 78 whereas the neutral dimeric complexes [U(C 8 H 8 )(dithiolene)] 2 were conveniently prepared by reaction of the borohydride precursor with the dithiocarbonates which are the protected forms of the dithiolene ligands, 79 and were converted into the Lewis base adducts [U(C 8 H 8 )(dithiolene)L 2 ] (L = py, hmpa, OPPh 3 ) (Scheme 10). 80 Polynuclear compounds attract a special attention for their structure and physical properties and also because they provide molecular models of condensed-matter systems containing f-elements. Reaction of UCl 4 with Li 2 fc•tmeda (fc = 1,1 -ferrocenylene) gave [Li 2 (py) 3 U(fc) 3 ], the first tris(1,1 -ferrocenylene) metal complex and the sole homoleptic metal bridged [1]ferrocenophane to have been crystallographically characterized (Fig.…”

Section: Synthesis and Reactivity Of Low-valent Actinide Compoundsmentioning

confidence: 99%

“…76,77The family of monocyclooctatetraene compounds has been enlarged with the introduction of the dithiolene ligand. The dianion [U(C 8 H 8 )(dddt) 2 ] 2− was obtained by treatment of [U(C 8 H 8 )-(BH 4 ) 2 )(THF)] with Na 2 dddt, 78 whereas the neutral dimeric complexes [U(C 8 H 8 )(dithiolene)] 2 were conveniently prepared by reaction of the borohydride precursor with the dithiocarbonates which are the protected forms of the dithiolene ligands,79 and were converted into the Lewis base adducts [U(C 8 H 8 )(dithiolene)L 2 ] (L = py, hmpa, OPPh 3 ) (Scheme 10) 80. Polynuclear compounds attract a special attention for their structure and physical properties and also because they provide molecular models of condensed-matter systems containing…”

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The vitality of uranium molecular chemistry at the dawn of the XXIst century

2006

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The intent of this Dalton Perspective is to highlight the recent advances in uranium molecular chemistry, with the results reported during the 2000-2006 period. This discipline is currently witnessing an impressive development, together with the theoretical chemistry and solid-state chemistry of the f-elements, and its face has profoundly changed, revealing unsuspected structural and reactivity features. This progress required and was facilitated by the use of new precursors. Studies of low-valent compounds gave a better insight into lanthanide(III)/actinide(III) differentiation and led to the discovery of unusual reactions, including activation of small molecules. A number of tetravalent uranium complexes, in particular polynuclear compounds, have been synthesized, which exhibit exciting structures and physicochemical properties. The potential of uranium(III) and uranium(IV) complexes in catalysis has been confirmed. The uranyl complexes, from mononuclear species to supramolecular assemblies, reveal a variety of novel structures, changing the generally accepted ideas on the coordination geometry and the stability of the UO2(2+) ion.

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Section: Synthesis and Reactivity Of Low-valent Actinide Compoundsmentioning

confidence: 99%

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confidence: 99%

The vitality of uranium molecular chemistry at the dawn of the XXIst century

2006

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“…[18] These cyclopentadienyl data all suggest that 6 is sterically crowded. 25] 1.938(4), 1.957(4) 30] 1.990, 1.998 [b, 27] 1.943 [27] 1.949 28] 1.957 [29] 1.96(2) [27] 2.005, 2.011 33] [29] 1. [27] 1…”

Section: Resultsmentioning

confidence: 99%

The Importance of a Single Methyl Group in Determining the Reaction Chemistry of Pentamethylcyclopentadienyl Cyclooctatetraenyl Uranium Metallocenes

Takase

Evans

2011

Chemistry A European J

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The steric factors that allow trivalent [(C(5)Me(5))(3)U] (1) to function as a three-electron reductant with C(8)H(8) to form tetravalent [{(C(5)Me(5))(C(8)H(8))U}(2)(μ-C(8)H(8))] (2) have been explored by examining the synthesis and reactivity of the intermediate, "[(C(5)Me(5))(2)(C(8)H(8))U]" (3), and the slightly less crowded analogues, [(C(5)Me(5))(C(5)Me(4)H)(C(8)H(8))U] and [(C(5)Me(4)H)(2)(C(8)H(8))U], that have, successively one less methyl group. The reaction of [{(C(5)Me(5))(C(8)H(8))U(μ-OTf)}(2)] (4; OTf=OSO(2) CF(3)) with two equivalents of KC(5)Me(5) in THF gave ring-opening to "[(C(5)Me(5))(C(8)H(8))U{O(CH(2))(4)(C(5) Me(5))}]" consistent with in situ formation of 3. Reaction of 4 with two and four equivalents of KC(5)Me(4)H generates two equivalents of [(C(5)Me(5))(C(5)Me(4)H)(C(8)H(8))U] (5) and [(C(5)Me(4)H)(2)(C(8)H(8))U] (6), respectively, which in contrast to 3 were isolable. Tetravalent 5 reduces phenazine and PhEEPh (E=S, Se, and Te) to form the tetravalent uranium reduction products, [{(C(5)Me(5))(C(8)H(8))U}(2)(μ-C(12)H(8)N(2))] (7), [{(C(5)Me(5))(C(8)H(8))U}(2)(μ-SPh)(2)] (8), [{(C(5)Me(5))(C(8)H(8))U}(2)(μ-SePh)(2)] (9), and [{(C(5)Me(5))(C(8)H(8))U}(2)(μ-TePh)(2)] (10), consistent with sterically induced reduction. In contrast, the less sterically crowded 6 does not react with these substrates.

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“…The structures show significant interaction between the metal and the CLC bond in the dithiolene (dithiolene = dddt, dmio, mdt). 160 A bent metal carbene geometry has been found in a uranium amido N-heterocyclic carbene complex (23), interpreted in terms of largely electrostatic contributions to the bonding. 161…”

Section: Actinidesmentioning

confidence: 99%

16 Scandium, yttrium, the lanthanides and the actinides

Cotton¹

2005

Annu. Rep. Prog. Chem., Sect. A

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Many interesting new results have been reported, both from the ''usual suspects'' (research groups of Evans, Ephritikhine, Lappert, Marks, Parker et al.) and from other groups, notably that of Mayer. Highlights this year include the synthesis of anhydrous uranyl iodide, following last year's report of hydrated uranyl iodide; remarkable addition reactions of a uranium(III) tris(aryloxide) including a complex of linear-bound CO 2 , and evidence for alkane co-ordination to an uranium (indeed, there seems to be much more interest in uranium chemistry as a whole); continued advances in organolanthanide catalysis; and more N 2 complexes of the lanthanides. And, of course, first reports have appeared concerning the syntheses of elements 113 and 115.

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Monocyclooctatetraenyl(dithiolene)uranium Compounds

Cited by 19 publications

References 46 publications

The vitality of uranium molecular chemistry at the dawn of the XXIst century

The vitality of uranium molecular chemistry at the dawn of the XXIst century

The Importance of a Single Methyl Group in Determining the Reaction Chemistry of Pentamethylcyclopentadienyl Cyclooctatetraenyl Uranium Metallocenes

16 Scandium, yttrium, the lanthanides and the actinides

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