Multi-electron reduction of sulfur and carbon disulfide using binuclear uranium(iii) borohydride complexes

Chemical Science
Polly L ArnoldJason B Love

Abstract

The first use of a dinuclear UIII/UIII complex in the activation of small molecules is reported. The octadentate Schiff-base pyrrole, anthracene-hinged 'Pacman' ligand LA combines two strongly reducing UIII centres and three borohydride ligands in [M(THF)4][{U(BH4)}2(μ-BH4)(LA)(THF)2] 1-M, (M = Li, Na, K). The two borohydride ligands bound to uranium outside the macrocyclic cleft are readily substituted by aryloxide ligands, resulting in a single, weakly-bound, encapsulated endo group 1 metal borohydride bridging the two UIII centres in [{U(OAr)}2(μ-MBH4)(LA)(THF)2] 2-M (OAr = OC6H2 t Bu3-2,4,6, M = Na, K). X-ray crystallographic analysis shows that, for 2-K, in addition to the endo-BH4 ligand the potassium counter-cation is also incorporated into the cleft through η5-interactions with the pyrrolides instead of extraneous donor solvent. As such, 2-K has a significantly higher solubility in non-polar solvents and a wider U-U separation compared to the 'ate' complex 1. The cooperative reducing capability of the two UIII centres now enforced by the large and relatively flexible macrocycle is compared for the two complexes, recognising that the borohydrides can provide additional reducing capability, and that the aryloxide-capped ...Continue Reading

References

Jan 10, 2002·Inorganic Chemistry·Anna KornienkoJohn G Brennan
Aug 9, 2002·Journal of the American Chemical Society·F Geoffrey N Cloke, Peter B Hitchcock
Sep 21, 2002·Chemical Communications : Chem Comm·A KayalS C Lee
Apr 3, 2003·Journal of the American Chemical Society·Joshua S Figueroa, Christopher C Cummins
Nov 1, 2003·Chemical Communications : Chem Comm·Gonzalo GivajaJason B Love
Dec 18, 2003·Journal of the American Chemical Society·Ingrid Castro-RodriguezKarsten Meyer
Sep 18, 2004·Science·Ingrid Castro-RodriguezKarsten Meyer
Aug 11, 2005·Journal of the American Chemical Society·Ingrid Castro-Rodriguez, Karsten Meyer
Sep 4, 2008·Inorganic Chemistry·Christopher D CarmichaelPolly L Arnold
Sep 19, 2008·Nature·Alexander R FoxChristopher C Cummins
Dec 23, 2008·Chemical Communications : Chem Comm·Owen T SummerscalesPeter B Hitchcock
Dec 2, 2009·Inorganic Chemistry·Liam P SpencerJames M Boncella
May 27, 2011·Chemical Communications : Chem Comm·Polly L Arnold
Jul 29, 2011·Journal of the American Chemical Society·Wenshan RenMarc D Walter
Jun 2, 2012·Proceedings of the National Academy of Sciences of the United States of America·Benedict M GardnerStephen T Liddle
Jul 24, 2012·Chemical Communications : Chem Comm·Anna-Corina SchmidtKarsten Meyer
Aug 28, 2012·Journal of the American Chemical Society·Jessie L BrownTrevor W Hayton
Sep 27, 2012·Journal of the American Chemical Society·Manolis J Manos, Mercouri G Kanatzidis
Oct 20, 2012·Chemical Society Reviews·Liandi WangZhengkun Yu
Nov 6, 2012·Angewandte Chemie·Victor MougelMarinella Mazzanti
Jul 9, 2014·Journal of the American Chemical Society·Polly L ArnoldJason B Love
Dec 2, 2014·Inorganic Chemistry·Danil E SmilesTrevor W Hayton
Dec 2, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Clément CampMarinella Mazzanti
Apr 18, 2015·Angewandte Chemie·Polly L ArnoldNikolas Kaltsoyannis

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Citations

Mar 15, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Aurélien R WillauerMarinella Mazzanti
Apr 9, 2019·Chemistry : a European Journal·Davide TonioloMarinella Mazzanti
Oct 15, 2019·Chemical Communications : Chem Comm·Luciano BarluzziMarinella Mazzanti
Jan 16, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Takuya AkaiShigeyuki Masaoka
Jan 19, 2020·International Journal of Molecular Sciences·Sokratis T TsantisSpyros P Perlepes
Apr 19, 2019·Chemical Science·Luciano BarluzziMarinella Mazzanti
Sep 25, 2017·Chemistry : a European Journal·Philipp Lang, Matthias Schwalbe
Mar 6, 2021·Acta Crystallographica. Section C, Structural Chemistry·Kurtis CarschTheodore A Betley
May 14, 2021·Inorganic Chemistry·Taylor V FetrowScott R Daly
Jan 23, 2019·Inorganic Chemistry·Daniel WernerPeter C Junk
Dec 12, 2018·Journal of the American Chemical Society·Ezra J CoughlinSuzanne C Bart
Apr 7, 2020·Journal of the American Chemical Society·Davide TonioloMarinella Mazzanti

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Methods Mentioned

BETA
X-ray
NMR

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