{
  "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.",
  "abstract_shown": true,
  "affiliations": [
    "State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry, Nanjing University Nanjing 210023 China manyi.yang@nju.edu.cn shuhua@nju.edu.cn.",
    "New Cornerstone Science Laboratory, Nanjing University Nanjing 210023 China.",
    "The Institute of Green Chemistry and Engineering, Nanjing University Suzhou 215163 China."
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 4,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Yining Zhang"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Guoao Li"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Manyi Yang"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Shuhua Li",
      "orcid": "0009-0006-4017-770X"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/bhwhz9hnxbv31.bib",
  "cited_by": 0,
  "doi": "10.1039/d6sc06455h",
  "fulltext_url": "https://europepmc.org/articles/PMC13711035",
  "id": "bhwhz9hnxbv31",
  "issns": [
    "2041-6520",
    "2041-6539"
  ],
  "landing_url": "https://europepmc.org/article/MED/42948357",
  "language": "eng",
  "licence": "CC-BY-NC",
  "licence_label": "CC BY-NC",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by-nc/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "Chemistry"
    ],
    [
      "openalex",
      "1605|Inorganic and Organometallic Chemistry"
    ]
  ],
  "openalex": "W7223059251",
  "pdf_url": "https://europepmc.org/articles/PMC13711035?pdf=render",
  "pmcid": "PMC13711035",
  "pmid": "42948357",
  "published": "2026-10-20",
  "publisher": "Royal Society of Chemistry",
  "ris": "https://research.draconitic.com/paper/bhwhz9hnxbv31.ris",
  "sources": [
    {
      "first_seen": "2026-10-31T00:20:34Z",
      "native_id": "MED:42948357",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42948357"
    },
    {
      "first_seen": "2026-10-31T12:21:53Z",
      "native_id": "PMC13711035",
      "source": "pmc",
      "url": "https://doi.org/10.1039/d6sc06455h"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Inorganic and Organometallic Chemistry",
      "subfield": "organic"
    }
  ],
  "title": "Dynamic metal-ligand coordination in solution: a ligand-exchange relay mechanism for gold(i) sulfido complex transformation.",
  "title_text": "Dynamic metal-ligand coordination in solution: a ligand-exchange relay mechanism for gold(i) sulfido complex transformation.",
  "type": "peer-reviewed",
  "updated_at": "2026-10-31T12:21:53Z",
  "url": "https://research.draconitic.com/paper/bhwhz9hnxbv31",
  "venue": "Chemical science",
  "versions": []
}