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Valence Bond Theory02:42

Valence Bond Theory

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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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Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine having a nitrogen atom as part of an aromatic ring has much less basicity than its corresponding alicyclic counterpart. For this reason, as presented in Figure 1, piperidine (pKb = 2.8) is significantly more basic than pyridine (pKb = 8.8).
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Aromatic Hydrocarbon Anions: Structural Overview01:18

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Neutral hydrocarbons like cyclopentadiene with an odd number of carbon atoms and one intervening CH2 group in the ring are not aromatic. Cyclopentadiene with 4 π electrons does not satisfy the 4n + 2 π electron rule. Additionally, the intervening CH2 group is sp3 hybridized and lacks a vacant p orbital, thereby interrupting the overlap of p orbitals in a continuous manner and preventing the delocalization of π electrons throughout the ring.
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Coordination Number and Geometry02:57

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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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Formation of Complex Ions03:45

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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Updated: Mar 30, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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Carbon dioxide is tightly bound in the [Co(Pyridine)(CO2)](-) anionic complex.

Jacob D Graham1, Allyson M Buytendyk1, Xinxing Zhang1

  • 1Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.

The Journal of Chemical Physics
|November 17, 2015
PubMed
Summary

Researchers studied the [Co(Pyridine)(CO2)](-) complex using photoelectron spectroscopy and DFT. They modeled CO2 binding to negatively charged sites in metal-organic frameworks, finding CO2 binds strongly to the cobalt complex.

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Area of Science:

  • Inorganic Chemistry
  • Computational Chemistry
  • Materials Science

Background:

  • Metal-organic frameworks (MOFs) are crucial in catalysis and gas storage.
  • Understanding CO2 binding to anionic sites in MOFs is key for carbon capture technologies.
  • Anionic cobalt complexes offer potential models for studying such interactions.

Purpose of the Study:

  • To investigate the electronic structure and CO2 binding of the [Co(Pyridine)(CO2)](-) anionic complex.
  • To establish this complex as a model system for CO2 interactions with negatively charged sites in MOFs.
  • To correlate experimental spectroscopic data with theoretical calculations.

Main Methods:

  • Photoelectron spectroscopy was employed to measure the vertical detachment energy (VDE).
  • Density functional theory (DFT) calculations were used to determine the complex's structure and binding energies.
  • Experimental VDE values were compared with calculated results for structural validation.

Main Results:

  • The measured VDE for [Co(Pyridine)(CO2)](-) was determined to be 2.7 eV.
  • DFT calculations predicted a structure with cobalt centrally bound to pyridine and CO2.
  • Calculated and experimental VDE values showed acceptable agreement, validating the proposed structure.
  • The binding energy of CO2 within the anionic complex was calculated to be 1.4 eV.

Conclusions:

  • The [Co(Pyridine)(CO2)](-) complex provides a viable model for studying CO2 binding to anionic sites.
  • The combination of photoelectron spectroscopy and DFT is effective for characterizing such anionic complexes.
  • The strong CO2 binding suggests potential applications in CO2 capture and related chemical processes.