{
  "abstract": "The Meerwein–Ponndorf–Verley (MPV) reaction has been used to probe the Lewis acidity and local environment of aluminum Lewis acid sites (LAS) in zeolites and how these properties evolve upon post-synthetic treatments such as calcination and steaming. However, directly linking catalytic activity to proposed framework-associated aluminum LAS remains challenging because the identity of the catalytically relevant species is often inferred indirectly from correlations between spectroscopic signatures and reactivity. Molecular mimics of heterogeneous active sites can test hypotheses related to structure and reactivity, yet there exists few scaffolds capable of faithfully recapitulating the primary coordination environments in zeolites under demanding catalytically relevant conditions. In this work, we report a molecular model of a framework-associated (SiO)3Al LAS supported by a rigid, tridentate tris(siloxide) ligand derived from truxenone. The model complex is a competent and robust catalyst for MPV transfer hydrogenation of benzaldehyde with iPrOH, and density functional theory calculations support a pathway initiated by protonation of a supporting siloxide ligand by iPrOH. In contrast, a structurally related anionic Al−OH complex was found to be inactive under the same conditions. These observations suggest that framework-associated (SiO)3Al LAS can mediate MPV reactivity and provide a molecular basis for metal–framework cooperativity occurring at Lewis acidic aluminum sites in zeolites.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry and Biochemistry",
    "University of California"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 4,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Martin-Louis Y. Riu",
      "orcid": "0000-0002-0900-3545"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Piper Szeliga"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Tyler A. Kerr",
      "orcid": "0000-0002-0369-4883"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Matthew Nava",
      "orcid": "0000-0001-6575-1153"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/fw2q3hbc9b8y7.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009397/v1",
  "fulltext_url": null,
  "id": "fw2q3hbc9b8y7",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009397/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1604|Zeolite Catalysis and Synthesis"
    ]
  ],
  "openalex": "W7214239689",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009397/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-23",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/fw2q3hbc9b8y7.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009397",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009397/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1604|Zeolite Catalysis and Synthesis",
      "subfield": "inorganic"
    }
  ],
  "title": "A Molecular View of Framework-Associated Zeolite Lewis Acid Sites: Linking Structure to Meerwein–Ponndorf–Verley Reactivity",
  "title_text": "A Molecular View of Framework-Associated Zeolite Lewis Acid Sites: Linking Structure to Meerwein–Ponndorf–Verley Reactivity",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/fw2q3hbc9b8y7",
  "venue": "ChemRxiv",
  "versions": []
}