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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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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...
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Proteins are dynamic macromolecules that carry out a wide variety of essential processes; however, the activities of most proteins depend on their interactions with other molecules or ions, known as ligands.
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Allosteric proteins have more than one ligand binding site; the binding of a ligand to any of these sites influences the binding of ligands to the other sites. When a protein is allosteric, its binding sites are called coupled or linked.  In the case of enzymes, the site that binds to the substrate is known as the active site and the other site is known as the regulatory site. When a ligand binds to the regulatory site, this leads to conformational changes in the protein that can influence...
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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Analyzing Protein Architectures and Protein-Ligand Complexes by Integrative Structural Mass Spectrometry
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Gold(I) Complexes Containing Phosphanyl- and Arsanylborane Ligands.

Jens Braese1, Alexander Schinabeck2, Michael Bodensteiner1

  • 1Universität Regensburg, Institut für Anorganische Chemie, 94053, Regensburg, Germany.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|May 31, 2018
PubMed
Summary

New gold(I) compounds with phosphanyl- and arsanylboranes were synthesized. Their structures reveal diverse aggregation behaviors, including dimers and chains, with luminescence observed in ionic complexes, linked to gold-gold distances.

Keywords:
arsenic ligandsaurophilic interactionsgoldluminescencephosphorus ligands

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Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Gold(I) complexes are known for their unique structural and photophysical properties.
  • Aurophilic interactions (Au-Au bonding) significantly influence the solid-state structures and luminescence of gold(I) compounds.
  • Pnictogen-borane ligands offer a versatile platform for tuning the properties of metal complexes.

Purpose of the Study:

  • To synthesize and characterize novel gold(I) complexes featuring phosphanyl- and arsanylborane ligands.
  • To investigate the impact of ligand structure on the solid-state aggregation and photophysical properties of these gold(I) compounds.
  • To explore the relationship between structural features, particularly aurophilic interactions, and luminescence behavior.

Main Methods:

  • Synthesis of gold(I) complexes via reactions of AuCl(tht) with various phosphanyl- and arsanylboranes.
  • Solid-state structural analysis using X-ray diffraction to determine aggregation patterns (dimers, chains, discrete molecules).
  • Photophysical characterization, including luminescence spectroscopy, and temperature-dependent studies.
  • Density Functional Theory (DFT) calculations to elucidate bonding and electronic structures.

Main Results:

  • Formation of neutral complexes [AuCl(RR'EBH2NMe3)] with diverse solid-state structures: dimers with aurophilic interactions, 1D chains, and discrete molecules.
  • Synthesis of ionic homoleptic complexes [Au(RR'EBH2NMe3)2][AlCl4] that exhibit luminescence.
  • Observed redshift in emission with decreasing temperature, correlating with shorter Au-Au distances in luminescent complexes.
  • DFT calculations provided insights into the electronic structure and bonding.

Conclusions:

  • The nature of the pnictogen atom (P vs. As) and organic substituents on the ligands dictates the solid-state aggregation of gold(I) complexes.
  • Ionic gold(I) complexes with these ligands can display temperature-dependent luminescence, influenced by aurophilic interactions.
  • These findings contribute to the understanding of structure-property relationships in gold(I) chemistry for potential optoelectronic applications.