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Switchable π-coordination and C–H metallation in small-cavity macrocyclic uranium and thorium complexes


Arnold, PL and Farnaby, JH and White, RC and Kaltsoyannis, N and Gardiner, MG and Love, JB, Switchable π-coordination and C-H metallation in small-cavity macrocyclic uranium and thorium complexes, Chemical Science, 5, (2) pp. 756-765. ISSN 2041-6520 (2014) [Refereed Article]


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Licensed under Creative Commons Attribution 3.0 Unported (CC BY 3.0)

DOI: doi:10.1039/c3sc52072b


New, conformationally restricted ThIV and UIV complexes, [ThCl2(L)] and [UI2(L)], of the small-cavity, dipyrrolide, dianionic macrocycle trans-calix[2]benzene[2]pyrrolide (L)2− are reported and are shown to have unusual κ55 binding in a bent metallocene-type structure. Single-electron reduction of [UI2(L)] affords [UI(THF)(L)] and results in a switch in ligand binding from κ5-pyrrolide to η6-arene sandwich coordination, demonstrating the preference for arene binding by the electron-rich UIII ion. Facile loss of THF from [UI(THF)(L)] further increases the amount of U–arene back donation. [UI(L)] can incorporate a further UIII equivalent, UI3, to form the very unusual dinuclear complex [U2I4(L)] in which the single macrocycle adopts both κ55 and η6161 binding modes in the same complex. Hybrid density functional theory calculations carried out to compare the electronic structures and bonding of [UIIII(L)] and [UIII2I4(L)] indicate increased contributions to the covalent bonding in [U2I4(L)] than in [UI(L)], and similar U–arene interactions in both. MO analysis and QTAIM calculations find minimal U–U interaction in [U2I4(L)]. In contrast to the reducible U complex, treatment of [ThCl2(L)] with either a reductant or non-nucleophilic base results in metallation of the aryl rings of the macrocycle to form the (L−2H)4− tetraanion and two new and robust Th–C bonds in the –ate complexes [K(THF)2ThIV(μ-Cl)(L−2H)]2 and K[ThIV{N(SiMe3)2}(L−2H)].

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:F-block chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Gardiner, MG (Associate Professor Michael Gardiner)
ID Code:93791
Year Published:2014
Web of Science® Times Cited:42
Deposited By:Chemistry
Deposited On:2014-08-18
Last Modified:2017-10-25
Downloads:381 View Download Statistics

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