μ-η6,η6-Arene-bridged diuranium hexakisketimide complexes isolable in two states of charge

Inorganic Chemistry
Paula L Diaconescu, Christopher C Cummins

Abstract

Diuranium μ-η(6),η(6)-arene complexes supported by ketimide ligands were synthesized and characterized. Disodium or dipotassium salts of the formula M(2)(μ-η(6),η(6)-arene)[U(NC(t)BuMes)(3)](2) (M = Na or K, Mes = 2,4,6-C(6)H(2)Me(3)) and monopotassium salts of the formula K(μ-η(6),η(6)-arene)[U(NC(t)BuMes)(3)](2) (arene = naphthalene, biphenyl, trans-stilbene, or p-terphenyl) were both observed. Two different salts of the monoanionic, toluene-bridged complexes are also described. Density functional theory calculations have been employed to illuminate the electronic structure of the μ-η(6),η(6)-arene diuranium complexes and to facilitate the comparison with related transition-metal systems, in particular (μ-η(6),η(6)-C(6)H(6))[VCp](2). It was found that the μ-η(6),η(6)-arene diuranium complexes were isolobal with (μ-η(6),η(6)-C(6)H(6))[VCp](2) and that the principal arene-binding interaction was a pair of δ bonds (total of 4e) involving both metals and the arene lowest unoccupied molecular orbital. Reactivity studies have been carried out with the mono- and dianionic μ-η(6),η(6)-arene diuranium complexes, revealing contrasting modes of redox chemistry as a function of the system's state of charge.

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Jun 27, 2002·Journal of the American Chemical Society·Paula L Diaconescu, Christopher C Cummins
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Citations

Feb 5, 2016·Journal of the American Chemical Society·Rami J BatriceMoris S Eisen
Feb 20, 2015·Inorganic Chemistry·Wenliang HuangPaula L Diaconescu
Aug 2, 2014·Inorganic Chemistry·Dominik P HalterKarsten Meyer
Nov 14, 2014·Journal of the American Chemical Society·Isabell S R KarmelMoris S Eisen
Aug 30, 2013·Journal of the American Chemical Society·Matthew R MacDonaldWilliam J Evans
Dec 17, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Paula L Diaconescu, Christopher C Cummins
Aug 8, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Wenliang Huang, Paula L Diaconescu
Feb 1, 2015·Chemical Science·Thomas L GianettiJohn Arnold
Feb 7, 2013·Nature Communications·Wenliang HuangPaula L Diaconescu
Aug 24, 2013·Nature Communications·Dipti PatelStephen T Liddle
Sep 7, 2017·Chemical Communications : Chem Comm·Andrea CauseroSjoerd Harder
Dec 3, 2017·Nature Communications·Benedict M GardnerStephen T Liddle
Jun 4, 2014·Angewandte Chemie·Henry S La PierreKarsten Meyer
Dec 10, 2013·Chemistry : a European Journal·Clément CampMarinella Mazzanti
Jun 21, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Ludovic CastroLaurent Maron
Jun 4, 2014·Angewandte Chemie·Henry S La PierreKarsten Meyer
Sep 23, 2014·Chemistry : a European Journal·Andrés FalcetoSantiago Alvarez
Nov 6, 2015·Chemistry : a European Journal·Maria A AntunesEugenio Coronado
Nov 6, 2012·Angewandte Chemie·Victor MougelMarinella Mazzanti
Dec 18, 2013·Chemical Communications : Chem Comm·Wenliang HuangPaula L Diaconescu
Apr 18, 2015·Angewandte Chemie·Polly L ArnoldNikolas Kaltsoyannis
Oct 13, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael A Boreen, John Arnold
May 20, 2021·Chemical Communications : Chem Comm·Shanmugam RevathiTapas Ghatak
Dec 15, 2020·Journal of the American Chemical Society·Chao YuWenliang Huang
Mar 21, 2019·Journal of the American Chemical Society·Michael A BoreenJohn Arnold
Jan 16, 2020·Journal of the American Chemical Society·Chad T PalumboMarinella Mazzanti
Jul 1, 2020·Inorganic Chemistry·Philip J CobbStephen T Liddle
Sep 19, 2019·Inorganic Chemistry·Alexander J AyresStephen T Liddle

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