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In 1923, G. N. Lewis proposed a generalized definition of acid-base behavior in which acids and bases are identified by their ability to accept or to donate a pair of electrons and form a coordinate covalent bond.
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This lesson delves into Lewis acids and bases in the context of the octet rule for electron-deficient compounds. Here, the concept is discussed, emphasizing the group 13 elements like boron or aluminium. Since group 13 elements possess three valence electrons, they form trivalent compounds with a sextet of electrons and a vacant orbital for the central atom. Consequently, these electron-deficient compounds accept electrons from other species to complete their octet in a chemical reaction. They...
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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
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Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy
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Alkane Coordination by a Neutral, Lewis Acidic Magnesium Complex.

Jeremy C Mullins1, Matthew J Evans1, Joseph M Parr1

  • 1School of Chemistry, Monash University, P.O. Box 23, Melbourne, Victoria 3800, Australia.

Journal of the American Chemical Society
|December 8, 2025
PubMed
Summary
This summary is machine-generated.

This study synthesizes novel magnesium diamide complexes that form the first group 2 metal-alkane/TMS complexes. These complexes exhibit weak but significant bonding, with electrostatic interactions dominating.

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Area of Science:

  • Organometallic Chemistry
  • Main Group Chemistry
  • Coordination Chemistry

Background:

  • Lewis acidic magnesium diamides with constrained geometries were synthesized.
  • X-ray crystallography revealed dimeric structures with intermolecular coordination.

Purpose of the Study:

  • To synthesize and characterize the first group 2 metal-alkane/TMS complexes.
  • To investigate the bonding interactions within these novel complexes.

Main Methods:

  • Synthesis of magnesium diamide complexes.
  • X-ray and neutron diffraction for structural determination.
  • Density Functional Theory (DFT) calculations, including ETS-NOCV and NBO analyses.
  • Non-covalent Interaction (NCI) and Quantum Theory of Atoms in Molecules (QTAIM) analyses.

Main Results:

  • Three new magnesium diamide complexes (1-3) were synthesized.
  • Complexes 1 and 2 adopted dimeric structures.
  • The first group 2 metal-alkane/TMS complexes (4-6) were formed by treating complex 1 with n-pentane, n-hexane, or tetramethylsilane (TMS).
  • Structural analysis confirmed the formulations of complexes 4-6.
  • DFT calculations indicated weak bonding between the alkane/TMS and magnesium fragment, comparable to transition metal complexes.
  • Electrostatic interactions were found to be the dominant bonding component (approx. 65%), with significant contributions from dispersion (approx. 20%) and orbital interactions (approx. 15%).

Conclusions:

  • The study reports the first examples of group 2 metal-alkane/TMS complexes.
  • Bonding in these complexes is characterized by a combination of electrostatic, dispersion, and orbital interactions.
  • The lipophilic coordination pocket influences dispersion forces, and charge flow from the alkane/TMS to magnesium contributes to orbital interactions.