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Unsupported Bonds between Copper(I) and Heavier Pnictogens.

Brandon T Watson1, Khadijatul Kobra Meem1, Vo Quang Huy Phan1

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Fluorinated poly(pyrazolyl)borate ligands stabilize copper(I) complexes with heavy pnictogens like antimony and bismuth. This research details novel copper-bismuthine complexes and analyzes group 15 trends, revealing insights into bonding and relativistic effects.

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Computational Chemistry

Background:

  • Stabilization of copper(I) complexes with heavy pnictogen donors is challenging.
  • Understanding trends in group 15 elements is crucial for designing new complexes.
  • Fluorinated ligands offer unique electronic properties for stabilizing reactive metal centers.

Purpose of the Study:

  • To synthesize and characterize copper(I) complexes with heavy pnictogen donors (Sb, Bi).
  • To investigate the role of fluorinated poly(pyrazolyl)borate ligands in stabilizing these complexes.
  • To analyze trends across group 15 elements in copper complexes and understand bonding characteristics.

Main Methods:

  • Synthesis of copper(I) complexes utilizing fluorinated poly(pyrazolyl)borate ligands.
  • Characterization of complexes via X-ray crystallography and spectroscopic methods.
  • Density Functional Theory (DFT) calculations to analyze bonding, stabilization energies, and electronic properties.

Main Results:

  • Successful stabilization of copper(I) complexes with triphenylarsine (AsPh3), triphenylstibine (SbPh3), and triphenylbismuthine (BiPh3).
  • Isolation of a novel copper-bismuthine complex with a direct, unsupported Cu-Bi bond.
  • DFT calculations reveal decreasing stabilization energy from P to Bi, highlighting relativistic effects and electrostatic dominance in Cu-E bonding.

Conclusions:

  • Fluorinated poly(pyrazolyl)borate ligands effectively stabilize copper(I) complexes with heavy pnictogen donors.
  • Relativistic effects significantly influence the bonding and Lewis basicity of heavier pnictogens.
  • The study provides fundamental insights into the coordination chemistry of heavy pnictogens with copper and the impact of ligand design.