This work provides new routes for the conversion of U(iv) into U(vi) bis(imido) complexes and offers new information on the manner in which the U(vi) compounds form. Many compounds from the series described by the general formula U(NR)(EPh)(L) (R = 2,6-diisopropylphenyl, tert-butyl; E = S, Se, Te; L = py, EPh) were synthesized via oxidation of an in situ generated U(iv) amido-imido species with PhE. This synthetic sequence provides a general route into bis(imido) U(vi) chalcogenolate complexes, circumventing the need to perform problematic salt metathesis reactions on U(vi) iodides. Investigation into the speciation of the U(iv) complexes that form prior to oxidation found a significant dependence on the identity of the ancillary ligands, with Bubpy forming the isolable imido-(bis)amido complex, U(NDipp)(NHDipp)(Bubpy). Together, these data are consistent with the view that the bis(imido) U(vi) motif - much like the uranyl ion, UO- is a thermodynamic sink into which simple ligand frameworks are unable to prevent uranium from falling when in the presence of a suitable retinue of imido proligands.
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We describe an example of a two-electron metal- and ligand-based reduction of MeSiN using uranium(iv) complexes with varying steric properties. Reaction of (CMe)U(CH)[P(SiMe)(Ph)] with MeSiN produces the imidophosphorane complex, (CMe)U(CH)[N[double bond, length as m-dash]P(SiMe)(Ph)] through oxidation of phosphorus. However, a similar reaction with a more sterically encumbering phosphido ligand, (CMe)U(CH)[P(SiMe)(Mes)] forms the U(iv) complex, (CMe)U[ -(,)-N(SiMe)P(Mes)N(SiMe)].
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The reduction of U(VI) to U(IV) is rare, especially in one step, and not observed electrochemically as a one-wave, two-electron couple. Here, we demonstrate that reduction of the uranium(VI) bis(imido) complex, (CMe)U[═N(4-OPrCH)], is readily accomplished with Al(CMe), forming the bridging uranium(IV)/aluminum(III) imido complex (CMe)U[μ-N(4-OPrCH)]Al(CMe). The structure and bonding of the bridging imido complex is examined with electrochemical measurements in tandem with density functional theory calculations.
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Dalton Trans
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Chemistry Division, Los Alamos National Laboratory, MS J514, Los Alamos, New Mexico 87545, USA.
This work provides new routes for the conversion of U(iv) into U(vi) bis(imido) complexes and offers new information on the manner in which the U(vi) compounds form. Many compounds from the series described by the general formula U(NR)(EPh)(L) (R = 2,6-diisopropylphenyl, tert-butyl; E = S, Se, Te; L = py, EPh) were synthesized via oxidation of an in situ generated U(iv) amido-imido species with PhE. This synthetic sequence provides a general route into bis(imido) U(vi) chalcogenolate complexes, circumventing the need to perform problematic salt metathesis reactions on U(vi) iodides.
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Dalton Trans
June 2018
Department of Chemistry, University of Missouri, Columbia, MO 65211, USA.
The first uranium(iii) phosphido complex is reported. The reaction of (C5Me5)2UI(THF) with KP[(C6H2Me3-2,4,6)(SiMe3)] affords (C5Me5)2U[P(C6H2Me3-2,4,6)(SiMe3)](THF), 1. The reactivity of 1 was explored with two equivalents of N3SiMe3 and N3Ad, Ad = adamantyl, both of which produce U(vi) bis(imido) complexes via four-electron reduction of the azides.
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