What is it about?
This study investigates how gold(I) forms stable complexes with large, polyaromatic phosphine ligands—molecules that have bulky, flat ring systems like naphthalene or anthracene. These ligands affect the geometry and properties of the gold complexes in unexpected ways. In particular, the study found that the bulky ligands can create sheltered molecular cavities where small guest molecules, such as chloroform, can bind to the gold-ethyne units via rare hydrogen–π interactions. Using NMR spectroscopy, crystallography, and newly developed methods for calculating spatial demand (cone angles), the paper provides new insights into how these ligands function and adapt in organometallic chemistry.
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Why is it important?
This work opened a new chapter in understanding how bulky phosphine ligands influence the behavior of metal complexes. It introduces the first complete series of gold(I) complexes with naphthyl and anthracenyl-substituted ligands and reveals rare hydrogen-bond-like interactions with solvent molecules, which had previously been only theoretically predicted. The paper also presents a practical, structure-based method to measure the steric impact of ligands (cone angles), offering a more realistic way to assess ligand space in real molecules. These findings help chemists better design catalysts and materials with tailored spatial and electronic properties.
Perspectives
This was one of my very first papers, summarizing part of my PhD research—and it still holds a special place for me. I’m still amazed that we uncovered these unique host–guest interactions: a new type of hydrogen bond involving chloroform and ethyne-gold units. At the time, it was surprising to observe such directional and specific binding in what seemed like a simple system. Looking back, this work helped initiate broader academic interest in unusual polar interactions—interactions that mimic hydrogen bonds and contribute significantly to the forces holding molecules together. It’s gratifying to know that our findings resonated with the field and helped spark ongoing research into non-canonical bonding phenomena.
Prof. Dr. Thomas Ernst Müller
Ruhr-Universitat Bochum
Read the Original
This page is a summary of: Complexes of gold(I) with polyaromatic phosphine ligands, Journal of Organometallic Chemistry, September 1995, Elsevier,
DOI: 10.1016/0022-328x(95)00517-t.
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