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Synthesis and Characterization of Functionalized Metal-organic Frameworks
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Mol-ecular structure of fac-[Mo(CO)3(DMSO)3].

Benedict J Elvers1, Christian Fischer1, Carola Schulzke1

  • 1Institut für Biochemie, Universität Greifswald, 4 Felix-Hausdorff-Straβe, 17489 Greifswald, Germany.

Acta Crystallographica. Section E, Crystallographic Communications
|May 24, 2021
PubMed
Summary

This study details the crystal structure of tri-carbonyl-tris-(dimethyl sulfoxide)-molybdenum, revealing a distorted octahedral geometry and facial isomer. Crystal packing is influenced by hydrogen bonding between dimethyl sulfoxide and carbonyl ligands.

Keywords:
carbonyl complexescrystal structurefac-coordinationmolybdenumsolvent complexes

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Area of Science:

  • Organometallic Chemistry
  • Crystallography
  • Coordination Chemistry

Background:

  • Molybdenum carbonyl complexes are important in catalysis and materials science.
  • Understanding the solid-state structure and bonding of such complexes is crucial for predicting their reactivity.
  • Dimethyl sulfoxide (DMSO) is a common ligand in coordination chemistry, but its role in molybdenum carbonyl complexes requires further investigation.

Purpose of the Study:

  • To characterize the crystal structure of tri-carbonyl-tris-(dimethyl sulfoxide)-molybdenum, [Mo(CO)3(DMSO)3].
  • To investigate the coordination geometry and isomerism of the molybdenum center.
  • To analyze the intermolecular interactions governing crystal packing.

Main Methods:

  • Single-crystal X-ray diffraction was used to determine the crystal structure.
  • Fourier-transform infrared (FT-IR) spectroscopy was employed to study the carbonyl ligand vibrations.
  • Analysis of bond lengths and angles provided insights into the coordination geometry.

Main Results:

  • The compound, fac-[Mo(CO)3(DMSO)3], crystallizes in the triclinic space group P with two molecules per unit cell.
  • A slightly distorted octahedral geometry was observed around the molybdenum center, with the facial isomer exclusively present.
  • Intermolecular hydrogen bonding between DMSO methyl groups and DMSO/carbonyl oxygen atoms stabilizes the crystal packing.

Conclusions:

  • The exclusive formation of the facial isomer is confirmed.
  • Intermolecular hydrogen bonding plays a significant role in the solid-state structure of this molybdenum complex.
  • Correlations between structural parameters (bond lengths) and FT-IR data provide a comprehensive understanding of the carbonyl ligands.