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Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
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Heterometallic Triply-Bridging Bis-Borylene Complexes.

Ranjit Bag1, Sourav Kar1, Suvam Saha1

  • 1Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600036, India.

Chemistry, an Asian Journal
|February 1, 2020
PubMed
Summary

This study reports new triply-bridging bis-{hydrido(borylene)} and bis-borylene metal complexes. These novel compounds, featuring transition metals from groups 6, 8, and 9, expand the understanding of borylene chemistry and metal-boron bonding.

Keywords:
borylenehydridometal carbonylmetallaboranetungsten

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Materials Science

Background:

  • Transition metal complexes with borylene ligands are of significant interest due to their unique bonding and reactivity.
  • The synthesis and characterization of novel borylene species can lead to new catalytic applications and materials.

Purpose of the Study:

  • To synthesize and characterize novel triply-bridging bis-{hydrido(borylene)} and bis-borylene species involving transition metals from groups 6, 8, and 9.
  • To investigate the electronic and structural properties of these new compounds, focusing on metal-boron and boron-hydrogen interactions.
  • To explore the reactivity and potential applications of these borylene complexes.

Main Methods:

  • Synthesis of borylene complexes via thermolysis of metal carbonyl precursors with boron-containing reagents.
  • Characterization using single-crystal X-ray diffraction, NMR (1H, 11B, 13C), IR spectroscopy, and mass spectrometry.
  • Computational analysis including frontier molecular orbital (HOMO-LUMO) calculations and chemical bonding analysis.

Main Results:

  • Successful synthesis of triply-bridging bis-{hydrido(borylene)} [(μ3-BH)2H2{Cp*W(CO)2}2{Fe(CO)2}] (1) and bis-borylene [(μ3-BH)2{Cp*W(CO)2}2{Fe(CO)3}] (2) complexes.
  • Chemical bonding analysis of 1 revealed stronger B-H interactions than M-H interactions.
  • Frontier molecular orbital analysis of 2 showed a larger HOMO-LUMO energy gap compared to 1.
  • Analogous bis-borylene complexes with Ruthenium (2') and Rhodium (3) were also synthesized, expanding the scope of these borylene species.

Conclusions:

  • The study successfully synthesized and characterized novel triply-bridging bis-{hydrido(borylene)} and bis-borylene complexes of W, Fe, Ru, and Rh.
  • The electronic and bonding properties were elucidated, highlighting the nature of metal-boron and B-H interactions.
  • These findings contribute to the fundamental understanding of borylene chemistry and open avenues for future research in organometallic chemistry.