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Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell. Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions.
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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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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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Divalent carbon(0) chemistry, part 1: Parent compounds.

Ralf Tonner1, Gernot Frenking

  • 1Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, Marburg, Germany.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|March 5, 2008
PubMed
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Quantum-chemical calculations reveal that carbodiphosphoranes and related compounds exhibit divalent carbon(0) characteristics due to donor-acceptor interactions. Even seemingly unsaturated molecules like tetraaminoallene function as masked divalent carbon(0) species.

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Area of Science:

  • Quantum Chemistry
  • Computational Chemistry
  • Inorganic Chemistry

Background:

  • Understanding the electronic structure and bonding in low-valent carbon compounds is crucial.
  • Carbodiphosphoranes and related molecules present unique bonding challenges.
  • Previous studies have explored various theoretical models for these systems.

Purpose of the Study:

  • To investigate the electronic structure and bonding in a series of L2C compounds.
  • To classify the oxidation state of the central carbon atom in these molecules.
  • To elucidate the nature of donor-acceptor interactions in these systems.

Main Methods:

  • Quantum-chemical calculations using Density Functional Theory (DFT) and ab initio methods (MP2, SCS-MP2, CCSD(T)).
  • Electronic structure analysis employing charge- and energy-partitioning methods.
  • Natural Bond Orbital (NBO) and Atoms in Molecules (AIM) analyses, along with Energy Decomposition Analysis (EDA).

Main Results:

  • Carbodiphosphoranes (L=PR3) are classified as divalent carbon(0) compounds, characterized by L-->C<--L donor-acceptor interactions.
  • Carbodicarbenes (L=NHC) and tetraaminoallene exhibit significant lone-pair character at the central carbon, suggesting they are "masked" divalent carbon(0) compounds.
  • Phosphoranylketene and carbon suboxide also display hidden double-lone-pair character.
  • Donor-acceptor bonds in these systems (L-->C) are approximately twice as strong as in L-->BH3 interactions.

Conclusions:

  • The bonding in L2C compounds can be effectively described by donor-acceptor interactions.
  • Several compounds previously considered unsaturated are reclassified as divalent carbon(0) or "masked" divalent carbon(0) species.
  • This provides a unified understanding of bonding in a range of low-valent carbon compounds.