Reversible temperature-induced polymorphic phase transitions of [Y(OAr)3] and [Ce(OAr)3] (Ar = 2,6-tBu2-4-MeC6H2): interconversions between pyramidal and planar geometries

Haddow, Mairi F.; Newland, Robert J.; Tegner, Bengt E.; Mansell, Stephen M.

doi:10.1039/c9ce00184k

CrystEngComm

2019

DOI: 10.1039/c9ce00184k

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Reversible temperature-induced polymorphic phase transitions of [Y(OAr)₃] and [Ce(OAr)₃] (Ar = 2,6-^tBu₂-4-MeC₆H₂): interconversions between pyramidal and planar geometries

Mairi F. Haddow

Robert J. Newland

Bengt E. Tegner

et al.

Abstract: Exploring the balance of energetics between planar and pyramidal forms of [Y(O-2,6-tBu2-4-MePh)3] and related complexes.

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Cited by 4 publications

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“…The study of uranium rather than rare earth MX 3 complexes enables us to explore all the potentially contributing factors hypothesised to favour pyramidalization. The actinide can make use of four different types of atomic orbitals (s, p, d and f) in metal-ligand bonding, in contrast to lanthanides, where f-orbital participation in bonding is tiny 22 .…”

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Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules

et al. 2022

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A range of reasons has been suggested for why many low-coordinate complexes across the periodic table exhibit a geometry that is bent, rather a higher symmetry that would best separate the ligands. The dominating reason or reasons are still debated. Here we show that two pyramidal UX3 molecules, in which X is a bulky anionic ligand, show opposite behaviour upon pressurisation in the solid state. UN″3 (UN3, N″ = N(SiMe3)2) increases in pyramidalization between ambient pressure and 4.08 GPa, while U(SAr)3 (US3, SAr = S-C6H2-tBu3−2,4,6) undergoes pressure-induced planarization. This capacity for planarization enables the use of X-ray structural and computational analyses to explore the four hypotheses normally put forward for this pyramidalization. The pyramidality of UN3, which increases with pressure, is favoured by increased dipole and reduction in molecular volume, the two factors outweighing the slight increase in metal-ligand agostic interactions that would be formed if it was planar. The ambient pressure pyramidal geometry of US3 is favoured by the induced dipole moment and agostic bond formation but these are weaker drivers than in UN3; the pressure-induced planarization of US3 is promoted by the lower molecular volume of US3 when it is planar compared to when it is pyramidal.

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Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules

et al. 2022

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One-step synthesis of heteroleptic rare-earth amide complexes featuring fluorenyl-tethered N-heterocyclic carbene ligands

et al. 2021

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Rare Earth Starting Materials and Methodologies for Synthetic Chemistry

Ortu

2022

Chem. Rev.

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The number of rare earth (RE) starting materials used in synthesis is staggering, ranging from simple binary metal-halide salts to borohydrides and “designer reagents” such as alkyl and organoaluminate complexes. This review collates the most important starting materials used in RE synthetic chemistry, including essential information on their preparations and uses in modern synthetic methodologies. The review is divided by starting material category and supporting ligands ( i.e. , metals as synthetic precursors, halides, borohydrides, nitrogen donors, oxygen donors, triflates, and organometallic reagents), and in each section relevant synthetic methodologies and applications are discussed.

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Reversible temperature-induced polymorphic phase transitions of [Y(OAr)₃] and [Ce(OAr)₃] (Ar = 2,6-^tBu₂-4-MeC₆H₂): interconversions between pyramidal and planar geometries

Abstract: Exploring the balance of energetics between planar and pyramidal forms of [Y(O-2,6-tBu2-4-MePh)3] and related complexes.

Cited by 4 publications

References 73 publications

Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules

Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules

One-step synthesis of heteroleptic rare-earth amide complexes featuring fluorenyl-tethered N-heterocyclic carbene ligands

Rare Earth Starting Materials and Methodologies for Synthetic Chemistry

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