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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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The double bond in a simple, unconjugated alkene is a region of high electron density that can act as a weak base or a nucleophile. The filled π orbital (HOMO) of the double bond can interact with the empty LUMO of an electrophile. A bonding interaction occurs when the electrophile attacks between the two carbons; the electrophile then accepts a pair of electrons from the π bond and undergoes addition across the double bond, yielding a single product.
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Olefins, which are unsaturated hydrocarbons containing one or more carbon–carbon double bonds, are broadly divided into alkenes and cycloalkenes. The general chemical formula of an alkene is CnH2n.
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Alkaline Earth-Olefin Complexes with Secondary Interactions.

Sorin-Claudiu Roşca1, Chiara Dinoi2,3, Elsa Caytan1

  • 1Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, Campus de Beaulieu, 263 avenue du Général Leclerc, 35042, Rennes Cedex, France.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|March 10, 2016
PubMed
Summary

New strontium and calcium complexes feature olefin coordination stabilized by unique alkaline earth interactions. These findings advance understanding of alkaline earth chemistry and non-covalent bonding in organometallic compounds.

Keywords:
alkaline earthscalciumcoordinated olefinsecondary interactionsstrontium

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Alkaline earth metals (e.g., strontium, calcium) are traditionally viewed as less versatile in coordination chemistry compared to transition metals.
  • Understanding non-covalent interactions is crucial for designing novel metal complexes with tailored properties.

Purpose of the Study:

  • To synthesize and characterize novel alkaline earth (Ae) olefin complexes.
  • To investigate the stabilizing roles of secondary alkaline earth-fluorine-carbon (Ae⋅⋅⋅F-C) and beta-agostic alkaline earth-hydrogen-silicon (Ae⋅⋅⋅H-Si) interactions.
  • To explore the thermodynamics and coordination behavior of olefins with alkaline earth centers.

Main Methods:

  • Synthesis of strontium and calcium complexes.
  • Solid-state structural analysis.
  • Nuclear Magnetic Resonance (NMR) spectroscopy.
  • Density Functional Theory (DFT) computations.

Main Results:

  • Stable olefin complexes of strontium and calcium were successfully synthesized and characterized.
  • Olefin coordination to alkaline earth metals was observed to be thermodynamically favorable over tetrahydrofuran (THF) coordination.
  • Secondary interactions (Ae⋅⋅⋅F-C and Ae⋅⋅⋅H-Si) were identified as key stabilizing factors.
  • DFT calculations confirmed the existence and significance of these Ae⋅⋅⋅olefin interactions and provided insights into coordination modes.

Conclusions:

  • Alkaline earth metals can form stable olefin complexes through specific non-covalent interactions.
  • These interactions offer alternative stabilization mechanisms in organometallic chemistry.
  • The study expands the known coordination chemistry of alkaline earth elements and highlights their potential in materials science.