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<p>Metal–ligand bonding interactions for <i>f</i>-element compounds are typically highly polarized with only minor covalent character. Whereas the 5<i>d</i>/6<i>d</i> orbitals are known to be chemically accessible for dative bonding, recent quantum chemical and spectroscopic analyses have indicated appreciable 4<i>f</i>/5<i>f</i>-orbital involvement in certain metal–ligand bonds. However, 4<i>f</i>-orbital covalency has not been compellingly linked to distinctive modes of chemical reactivity via rigorous comparative study and mechanistic investigation. Here a series of M<sup>IV</sup>–cyclopropenyl complexes (M = Ti, Zr, Ce, Hf, Th) are described, wherein the cerium congener exhibits a 4<i>f</i>-covalent Ce=C<sub>α</sub> interaction, causing a ring-opening isomerization reaction through a single-crystal-to-single-crystal transformation. The results provide evidence for 4<i>f</i>-orbital covalency by demonstrating its expression in the reactivity of an <i>f</i>-element complex within an isostructural series of tetravalent <i>d</i>- and <i>f</i>-block metal complexes. They also provide new directions for the study of orbital covalency effects of molecular compounds in solid-state chemical transformations.</p><p></p>

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4f-orbital covalency enables a single-crystal-to-single-crystal ring-opening isomerization in a CeIV–cyclopropenyl complex

  • 期刊论文

  • 发表日期：

    2025年4月23日

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  • Brett D. Vincenzini,
  • Xiaojuan Yu,
  • Sébastien Paloc,
  • Patrick W. Smith,
  • Himanshu Gupta,
  • Pragati Pandey,
  • Greggory T. Kent,
  • Osvaldo Ordonez,
  • Taylor Keller,
  • Michael R. Gau,
  • Alexandra M. Bacon,
  • Stefan G. Minasian,
  • Trevor W. Hayton,
  • Jochen Autschbach,
  • Eric J. Schelter

摘要

Metal–ligand bonding interactions for f-element compounds are typically highly polarized with only minor covalent character. Whereas the 5d/6d orbitals are known to be chemically accessible for dative bonding, recent quantum chemical and spectroscopic analyses have indicated appreciable 4f/5f-orbital involvement in certain metal–ligand bonds. However, 4f-orbital covalency has not been compellingly linked to distinctive modes of chemical reactivity via rigorous comparative study and mechanistic investigation. Here a series of MIV–cyclopropenyl complexes (M = Ti, Zr, Ce, Hf, Th) are described, wherein the cerium congener exhibits a 4f-covalent Ce=Cα interaction, causing a ring-opening isomerization reaction through a single-crystal-to-single-crystal transformation. The results provide evidence for 4f-orbital covalency by demonstrating its expression in the reactivity of an f-element complex within an isostructural series of tetravalent d- and f-block metal complexes. They also provide new directions for the study of orbital covalency effects of molecular compounds in solid-state chemical transformations.