Emergence of comparable covalency in isostructural cerium(iv)- and uranium(iv)-carbon multiple bonds

Chemical Science
Matthew GregsonStephen T Liddle

Abstract

We report comparable levels of covalency in cerium- and uranium-carbon multiple bonds in the iso-structural carbene complexes [M(BIPMTMS)(ODipp)2] [M = Ce (1), U (2), Th (3); BIPMTMS = C(PPh2NSiMe3)2; Dipp = C6H3-2,6-iPr2] whereas for M = Th the M[double bond, length as m-dash]C bond interaction is much more ionic. On the basis of single crystal X-ray diffraction, NMR, IR, EPR, and XANES spectroscopies, and SQUID magnetometry complexes 1-3 are confirmed formally as bona fide metal(iv) complexes. In order to avoid the deficiencies of orbital-based theoretical analysis approaches we probed the bonding of 1-3via analysis of RASSCF- and CASSCF-derived densities that explicitly treats the orbital energy near-degeneracy and overlap contributions to covalency. For these complexes similar levels of covalency are found for cerium(iv) and uranium(iv), whereas thorium(iv) is found to be more ionic, and this trend is independently found in all computational methods employed. The computationally determined trends in covalency of these systems of Ce ∼ U > Th are also reproduced in experimental exchange reactions of 1-3 with MCl4 salts where 1 and 2 do not exchange with ThCl4, but 3 does exchange with MCl4 (M = Ce, U) and 1 and 2 react with U...Continue Reading

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Citations

Aug 25, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Qun-Yan WuWei-Qun Shi
Sep 30, 2016·Nature Communications·Elizabeth P WildmanStephen T Liddle
Feb 6, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Victoria E J BerrymanNikolas Kaltsoyannis
Apr 6, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael W RosenzweigKarsten Meyer
Dec 17, 2019·Angewandte Chemie·Aurélien R WillauerMarinella Mazzanti
Jun 5, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael A BoreenJohn Arnold
Jul 15, 2020·Physical Chemistry Chemical Physics : PCCP·Victoria E J BerrymanNikolas Kaltsoyannis
Sep 15, 2019·Nature Communications·Jingzhen DuStephen T Liddle
Mar 14, 2018·Angewandte Chemie·Erli LuStephen T Liddle
Feb 6, 2017·Nature Communications·Matthew GregsonStephen T Liddle
Feb 9, 2019·Nature Communications·Erli LuStephen T Liddle
Aug 28, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Wai-Man CheungWa-Hung Leung
Oct 3, 2019·IUCrJ·Christopher G GianopoulosA Alan Pinkerton
Mar 10, 2017·Nature Communications·Elizabeth P WildmanStephen T Liddle
Sep 30, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Stephan HohlochJohn Arnold
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Feb 11, 2021·Chemistry : a European Journal·Dumitru-Claudiu SergentuJochen Autschbach
Jun 2, 2021·Chemical Communications : Chem Comm·Nathan DavisonErli Lu
Feb 5, 2020·Chemical Science·Danil E SmilesTolek Tyliszczak
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Methods Mentioned

BETA
X-ray
electron paramagnetic resonance
NMR

Software Mentioned

Amsterdam Density Functional ( ADF ) suite
AIMAll
RASSCF
MOLEKEL
MOLCAS
TURBOMOLE

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