{
  "abstract": "Off-cycle species are typically considered detrimental to catalytic activity; however, a dormant form can also extend catalyst lifetime. This study shows under which conditions a reversible off-cycle reservoir can increase the turnover number (TON) of a homogeneous catalyst. When both turnover and all deactivation steps are first order in catalyst, branching remains constant over time and the reservoir only holds the catalyst in a dormant state, the distribution of turnovers per catalyst does not change, regardless of the number of reservoirs. The reaction is slowed, and under an external clock, such as a poison that forms independently of the catalyst, the TON decreases. When deactivation is of higher order in catalyst than turnover, a fast reservoir of depth acts as a -fold dilution. This increases the TON up to a ceiling set by the first-order deactivation pathways, and for a given batch time there is an optimal depth. In the published model of (DTBM-SEGPHOS)CuH, the HBpin adduct protects the catalyst from aggregation but is 2.9–5.9 times deeper than optimal. In Hoveyda–Grubbs metathesis, a styrenyl-ether reservoir slows the reaction threefold without reducing the TON. A reservoir can be beneficial only if the catalyst-limited TON decreases as catalyst loading increases, that is, if the slope of log TON against log loading is negative. Dilution experiments and a series with graded amounts of additive then show whether it will be.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, Belgium, 3001"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 1,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Joshua M. Sims",
      "orcid": "0000-0002-8279-3010"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/046kbqq6zcrhx.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010890/v1",
  "fulltext_url": null,
  "id": "046kbqq6zcrhx",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010890/v1",
  "language": null,
  "licence": "CC-BY-NC-ND",
  "licence_label": "CC BY-NC-ND",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Organometallic Complex Synthesis and Catalysis"
    ]
  ],
  "openalex": "W7223177190",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010890/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-22",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/046kbqq6zcrhx.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:26Z",
      "native_id": "10.26434/chemrxiv.15010890",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010890/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Organometallic Complex Synthesis and Catalysis",
      "subfield": "organic"
    }
  ],
  "title": "When Can an Off-Cycle Reservoir Raise a Catalyst’s Turnover Number?",
  "title_text": "When Can an Off-Cycle Reservoir Raise a Catalyst’s Turnover Number?",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:26Z",
  "url": "https://research.draconitic.com/paper/046kbqq6zcrhx",
  "venue": "ChemRxiv",
  "versions": []
}