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Emergence of comparable covalency in isostructural cerium(IV)– and uranium(IV)–carbon multiple bonds

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Emergence of comparable covalency in isostructural cerium(IV)– and uranium(IV)–carbon multiple bonds. / Gregson, Matthew; Lu, Erli; McInnes, Eric; Hennig, Cristoph; Scheinost, Andreas; McMaster, Jonathan; Lewis, William; Blake, Alexander; Kerridge, Andrew; Liddle, Stephen.

In: Chemical Science, Vol. 7, No. 5, 01.05.2016, p. 3286-3297.

Research output: Contribution to journalJournal article

Harvard

Gregson, M, Lu, E, McInnes, E, Hennig, C, Scheinost, A, McMaster, J, Lewis, W, Blake, A, Kerridge, A & Liddle, S 2016, 'Emergence of comparable covalency in isostructural cerium(IV)– and uranium(IV)–carbon multiple bonds', Chemical Science, vol. 7, no. 5, pp. 3286-3297. https://doi.org/10.1039/C6SC00278A

APA

Gregson, M., Lu, E., McInnes, E., Hennig, C., Scheinost, A., McMaster, J., ... Liddle, S. (2016). Emergence of comparable covalency in isostructural cerium(IV)– and uranium(IV)–carbon multiple bonds. Chemical Science, 7(5), 3286-3297. https://doi.org/10.1039/C6SC00278A

Vancouver

Gregson M, Lu E, McInnes E, Hennig C, Scheinost A, McMaster J et al. Emergence of comparable covalency in isostructural cerium(IV)– and uranium(IV)–carbon multiple bonds. Chemical Science. 2016 May 1;7(5):3286-3297. https://doi.org/10.1039/C6SC00278A

Author

Gregson, Matthew ; Lu, Erli ; McInnes, Eric ; Hennig, Cristoph ; Scheinost, Andreas ; McMaster, Jonathan ; Lewis, William ; Blake, Alexander ; Kerridge, Andrew ; Liddle, Stephen. / Emergence of comparable covalency in isostructural cerium(IV)– and uranium(IV)–carbon multiple bonds. In: Chemical Science. 2016 ; Vol. 7, No. 5. pp. 3286-3297.

Bibtex

@article{89a76aa8df714e96a41ba49ec145d5ef,
title = "Emergence of comparable covalency in isostructural cerium(IV)– and uranium(IV)–carbon multiple bonds",
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 1–3 via 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 UCl4 and CeCl4, respectively, to establish equilibria. This study therefore provides complementary theoretical and experimental evidence that contrasts to the accepted description that generally lanthanide–ligand bonding in non-zero oxidation state complexes is overwhelmingly ionic but that of uranium is more covalent.",
author = "Matthew Gregson and Erli Lu and Eric McInnes and Cristoph Hennig and Andreas Scheinost and Jonathan McMaster and William Lewis and Alexander Blake and Andrew Kerridge and Stephen Liddle",
year = "2016",
month = "5",
day = "1",
doi = "10.1039/C6SC00278A",
language = "English",
volume = "7",
pages = "3286--3297",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "5",

}

RIS

TY - JOUR

T1 - Emergence of comparable covalency in isostructural cerium(IV)– and uranium(IV)–carbon multiple bonds

AU - Gregson, Matthew

AU - Lu, Erli

AU - McInnes, Eric

AU - Hennig, Cristoph

AU - Scheinost, Andreas

AU - McMaster, Jonathan

AU - Lewis, William

AU - Blake, Alexander

AU - Kerridge, Andrew

AU - Liddle, Stephen

PY - 2016/5/1

Y1 - 2016/5/1

N2 - 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 1–3 via 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 UCl4 and CeCl4, respectively, to establish equilibria. This study therefore provides complementary theoretical and experimental evidence that contrasts to the accepted description that generally lanthanide–ligand bonding in non-zero oxidation state complexes is overwhelmingly ionic but that of uranium is more covalent.

AB - 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 1–3 via 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 UCl4 and CeCl4, respectively, to establish equilibria. This study therefore provides complementary theoretical and experimental evidence that contrasts to the accepted description that generally lanthanide–ligand bonding in non-zero oxidation state complexes is overwhelmingly ionic but that of uranium is more covalent.

U2 - 10.1039/C6SC00278A

DO - 10.1039/C6SC00278A

M3 - Journal article

VL - 7

SP - 3286

EP - 3297

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 5

ER -