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Related Concept Videos

MO Theory and Covalent Bonding02:40

MO Theory and Covalent Bonding

The molecular orbital theory describes the distribution of electrons in molecules in a manner similar to the distribution of electrons in atomic orbitals. The region of space in which a valence electron in a molecule is likely to be found is called a molecular orbital. Mathematically, the linear combination of atomic orbitals (LCAO) generates molecular orbitals. Combinations of in-phase atomic orbital wave functions result in regions with a high probability of electron density, while...
Hückel's Rule Diagram of π MOs: Frost Circle01:08

Hückel's Rule Diagram of π MOs: Frost Circle

The Frost circle or the inscribed polygon method is a graphical method for determining the relative energies of π molecular orbitals (MOs) for planar, fully conjugated, and monocyclic compounds. This method was first described by A. A. Frost and Boris Musulin in 1953.
A Frost circle is constructed by drawing a polygon whose number of edges is equal to the number of carbons of the given cyclic system, with one of the vertices pointing down. Then, a circle is drawn enclosing the polygon so that...
Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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...
Frost Circles for Different Conjugated Systems01:18

Frost Circles for Different Conjugated Systems

The inscribed polygon method is consistent with Hückel’s 4n + 2 rule and helps to learn whether the given cyclic compound is aromatic or not. The compound is stable and aromatic if every bonding molecular orbital (MO) is completely filled with a pair of electrons. However, if the non-bonding or antibonding orbitals are filled with electrons, the compound is unstable and not aromatic. Consider the Frost circle diagrams for cycloalkenes containing 4 to 8 carbons.

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Related Experiment Video

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Synthesis and Characterization of Functionalized Metal-organic Frameworks
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Published on: September 5, 2014

Synthesis, characterization, and computational study of MoSF4.

Jared Nieboer1, Johnathan P Mack, Hélène P A Mercier

  • 1Department of Chemistry and Biochemistry, The University of Lethbridge, Lethbridge, Alberta T1K 3M4, Canada.

Inorganic Chemistry
|June 10, 2010
PubMed
Summary

Molybdenum sulfide tetrafluoride (MoSF4) was synthesized and characterized, revealing infinite fluorine-bridged chains in its crystal structure. Quantum-chemical calculations aided in understanding its vibrational spectra and bonding.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Computational Chemistry

Background:

  • Molybdenum compounds exhibit diverse coordination chemistries.
  • Fluoride and sulfide ligands play crucial roles in transition metal complex structures.
  • Understanding the synthesis and properties of novel molybdenum compounds is essential for materials development.

Purpose of the Study:

  • To synthesize and fully characterize molybdenum sulfide tetrafluoride (MoSF4).
  • To elucidate the structural and bonding properties of MoSF4 in both solid and gas phases.
  • To correlate experimental spectroscopic data with theoretical calculations.

Main Methods:

  • Synthesis of MoSF4 from MoF6 and S(Si(CH3)3)2 in CFCl3.
  • Characterization using Raman, infrared, and 19F NMR spectroscopy.
  • X-ray crystallography for crystal structure determination.
  • Quantum-chemical calculations (B3LYP, PBE1PBE) for gas-phase geometry and vibrational frequencies.
  • Natural bond order analysis.

Main Results:

  • Successful synthesis and comprehensive characterization of MoSF4.
  • Crystal structure revealed infinite fluorine-bridged chains of MoSF4 units.
  • Quantum-chemical calculations provided insights into monomeric MoSF4 and (MoSF4)3F- species.
  • Vibrational frequencies from calculations aided in assigning experimental spectra.
  • Natural bond order analysis compared bonding in MoSF4 and WSF4.

Conclusions:

  • MoSF4 forms extended fluorine-bridged polymeric chains in the solid state.
  • Computational methods are valuable tools for interpreting the spectroscopy of MoSF4.
  • The study provides a detailed understanding of the structure and bonding in MoSF4.