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Related Concept Videos

Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Valence Bond Theory02:42

Valence Bond Theory

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...
Valence Bond Theory02:45

Valence Bond Theory

Overview of Valence Bond Theory
Coordination Compounds and Nomenclature02:54

Coordination Compounds and Nomenclature

In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
Electron Carriers01:24

Electron Carriers

Electron carriers can be thought of as electron shuttles. These compounds can easily accept electrons (i.e., be reduced) or lose them (i.e., be oxidized). They play an essential role in energy production because cellular respiration is contingent on the flow of electrons.
Over the many stages of cellular respiration, glucose breaks down into carbon dioxide and water. Electron carriers pick up electrons lost by glucose in these reactions, temporarily storing and releasing them into the electron...
Role of Reduced Coenzymes NADH and FADH₂01:29

Role of Reduced Coenzymes NADH and FADH₂

The energy released from the breakdown of the chemical bonds within nutrients can be stored either through the reduction of electron carriers or in the bonds of adenosine triphosphate (ATP). In living systems, a small class of compounds functions as mobile electron carriers, molecules that bind to and shuttle high-energy electrons between compounds in pathways. The principal electron carriers that will be considered originate from the B vitamin group and are derivatives of nucleotides; they are...

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Related Experiment Video

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Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
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Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

Energy transport via coordination bonds.

Valeriy M Kasyanenko1, Zhiwei Lin, Grigory I Rubtsov

  • 1Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA.

The Journal of Chemical Physics
|June 24, 2010
PubMed
Summary

Vibrational energy transport across coordination bonds in iron complexes was studied. The relaxation-assisted two-dimensional infrared (RA 2DIR) technique revealed significant energy amplification, demonstrating its utility for molecular structure analysis.

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Area of Science:

  • Chemical Physics
  • Molecular Spectroscopy
  • Coordination Chemistry

Background:

  • Vibrational energy transport in transition metal complexes occurs across weak coordination bonds.
  • Understanding this transport is crucial for molecular-level insights and the relaxation-assisted two-dimensional infrared (RA 2DIR) technique.
  • The RA 2DIR technique links vibrational population transport time to molecular distance.

Purpose of the Study:

  • To investigate energy transport across coordination bonds in a specific iron complex.
  • To demonstrate the applicability of dual-frequency RA 2DIR spectroscopy for studying vibrational energy dynamics.
  • To correlate energy transport times with intermode distances for structural interrogation.

Main Methods:

  • Utilized dual-frequency relaxation-assisted two-dimensional infrared (RA 2DIR) spectroscopy.
  • Examined vibrational energy transport in tetraethylammonium bis(maleonitriledithiolate)iron(III)nitrosyl complex.
  • Interrogated three specific mode pairs: C≡N/N=O, N=O/C≡N, and N=O/C-C.

Main Results:

  • Observed substantial cross-peak amplification due to vibrational energy transport, with a record 27-fold amplification for C≡N/N=O.
  • Demonstrated that lower frequency modes can act as energy acceptors, even when the probed mode has a higher frequency.
  • A ninefold amplification for N=O/C≡N confirmed that excitation of the probed mode is not essential for strong cross-peaks.

Conclusions:

  • Vibrational energy transport across coordination bonds in iron complexes is significant and measurable.
  • The RA 2DIR technique is effective for structural interrogation of transition metal complexes.
  • A correlation between energy transport time and intermode distance was established, validating the RA 2DIR method's structural sensitivity.