Dynamic metal-ligand coordination in solution: a ligand-exchange relay mechanism for gold(i) sulfido complex transformation.
- 1State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry, Nanjing University Nanjing 210023 China [email protected] [email protected].
- 2New Cornerstone Science Laboratory, Nanjing University Nanjing 210023 China.
- 3The Institute of Green Chemistry and Engineering, Nanjing University Suzhou 215163 China.
Abstract
Understanding dynamic metal-ligand interactions in polynuclear metal complexes is essential to control their structures and reactivities, yet the underlying mechanisms remain elusive because key intermediates are short-lived and often spectroscopically silent. Here we combine ab initio-accurate machine-learning interatomic potentials (MLPs) with on-the-fly probability enhanced sampling (OPES) in molecular dynamics (MD) simulations to resolve such solution-phase transformations. Using the interconversion of phosphine-ligated gold(i) sulfido complexes, [Au₁₀S₄(L)₄]²⁺ ⇌ 2 [Au₅S₂(L)₂]⁺ (L = LPh or LTh), as a prototypical system, we uncover a ligand-exchange relay mechanism mediated by (µ₄-S)-Au-(µ₃-S) motifs. Au-P bond cleavage triggers successive phosphine-exchange steps that relay electrophilic character across equatorial Au atoms, during which dynamic η ²-arene-Au interactions stabilize the electrophilic centers. Free-energy analysis shows that the decanuclear complexes are thermodynamically favored over the corresponding pentanuclear products and that the maximum barrier is lower for LPh-ligated than for LTh-ligated systems, approximately 130 vs. 167 kJ mol⁻¹, consistent with experimental observations. This ligand dependence arises from the P-P bite distance, which controls key Au-S contacts and thereby the relay-intermediate stability. These findings reveal ligand-exchange relay as a distinct dynamic coordination mode and demonstrate that MLP-driven enhanced-sampling simulations can resolve interconversions of polynuclear complexes with atomistic and free-energy resolution.
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BibTeX
@article{zhang2026dynamic,
title = {{Dynamic metal-ligand coordination in solution: a ligand-exchange relay mechanism for gold(i) sulfido complex transformation.}},
author = {Yining Zhang and Guoao Li and Manyi Yang and Shuhua Li},
journal = {Chemical science},
year = {2026},
month = oct,
doi = {10.1039/d6sc06455h},
url = {https://europepmc.org/article/MED/42948357},
note = {CC BY-NC},
}
RIS
TY - JOUR
TI - Dynamic metal-ligand coordination in solution: a ligand-exchange relay mechanism for gold(i) sulfido complex transformation.
AU - Yining Zhang
AU - Guoao Li
AU - Manyi Yang
AU - Shuhua Li
PY - 2026
DA - 2026/10/20
JO - Chemical science
DO - 10.1039/d6sc06455h
UR - https://europepmc.org/article/MED/42948357
AB - Understanding dynamic metal-ligand interactions in polynuclear metal complexes is essential to control their structures and reactivities, yet the underlying mechanisms remain elusive because key intermediates are short-lived and often spectroscopically silent. Here we combine ab initio-accurate machine-learning interatomic potentials (MLPs) with on-the-fly probability enhanced sampling (OPES) in molecular dynamics (MD) simulations to resolve such solution-phase transformations. Using the interconversion of phosphine-ligated gold(i) sulfido complexes, [Au₁₀S₄(L)₄]²⁺ ⇌ 2 [Au₅S₂(L)₂]⁺ (L = LPh or LTh), as a prototypical system, we uncover a ligand-exchange relay mechanism mediated by (µ₄-S)-Au-(µ₃-S) motifs. Au-P bond cleavage triggers successive phosphine-exchange steps that relay electrophilic character across equatorial Au atoms, during which dynamic η ²-arene-Au interactions stabilize the electrophilic centers. Free-energy analysis shows that the decanuclear complexes are thermodynamically favored over the corresponding pentanuclear products and that the maximum barrier is lower for LPh-ligated than for LTh-ligated systems, approximately 130 vs. 167 kJ mol⁻¹, consistent with experimental observations. This ligand dependence arises from the P-P bite distance, which controls key Au-S contacts and thereby the relay-intermediate stability. These findings reveal ligand-exchange relay as a distinct dynamic coordination mode and demonstrate that MLP-driven enhanced-sampling simulations can resolve interconversions of polynuclear complexes with atomistic and free-energy resolution.
SN - 2041-6520
SN - 2041-6539
ER -