{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T05:10:19Z","timestamp":1788844219436,"version":"build-2803163510"},"reference-count":112,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,9,7]],"date-time":"2026-09-07T00:00:00Z","timestamp":1788739200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,9,7]],"date-time":"2026-09-07T00:00:00Z","timestamp":1788739200000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The syntheses of frustrated Lewis pairs (FLPs) based on a 4,5\u2010difunctionalised xanthene backbone, and featuring the pentachlorophenyl\u2010containing boryl groups, are reported. At a general level, this allows for systematic comparison of these systems in H\n                    <jats:sub>2<\/jats:sub>\n                    activation as a function of the Lewis acid component, both internally and with respect to B(C\n                    <jats:sub>6<\/jats:sub>\n                    F\n                    <jats:sub>5<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    \u2010containing FLPs. Incorporation of C\n                    <jats:sub>6<\/jats:sub>\n                    Cl\n                    <jats:sub>5<\/jats:sub>\n                    groups over C\n                    <jats:sub>6<\/jats:sub>\n                    F\n                    <jats:sub>5<\/jats:sub>\n                    diminishes the thermodynamic ability of these systems to activate H\n                    <jats:sub>2<\/jats:sub>\n                    , reflecting greater steric bulk and a disincentivized pyramidal geometry at boron. Di\n                    <jats:italic>iso<\/jats:italic>\n                    propylphosphino systems featuring \u2013B(C\n                    <jats:sub>6<\/jats:sub>\n                    Cl\n                    <jats:sub>5<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    and \u2013B(C\n                    <jats:sub>6<\/jats:sub>\n                    Cl\n                    <jats:sub>5<\/jats:sub>\n                    )(C\n                    <jats:sub>6<\/jats:sub>\n                    F\n                    <jats:sub>5<\/jats:sub>\n                    ) groups activate dihydrogen reversibly at room temperature; solution\u2010phase VT\u2010NMR studies, however, uncover unprecedented behavior at lower temperatures. On cooling, the extent of H\n                    <jats:sub>2<\/jats:sub>\n                    uptake first increases (due to the reduced magnitude of the unfavorable\n                    <jats:italic>T<\/jats:italic>\n                    \u0394\n                    <jats:italic>S<\/jats:italic>\n                    \u00b0 term); at even lower temperatures, phosphonium\u2010borate formation is forced to compete with intermolecular FLP aggregation via aromatic stacking between the C\n                    <jats:sub>6<\/jats:sub>\n                    Cl\n                    <jats:sub>5<\/jats:sub>\n                    rings. This leads to the observation of V\u2010shaped van't Hoff plots with inflection points at 263 K (for xanth(PiPr\n                    <jats:sub>2<\/jats:sub>\n                    ){B(C\n                    <jats:sub>6<\/jats:sub>\n                    Cl\n                    <jats:sub>5<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    }) and 268 K (for xanth(PiPr\n                    <jats:sub>2<\/jats:sub>\n                    ){B(C\n                    <jats:sub>6<\/jats:sub>\n                    Cl\n                    <jats:sub>5<\/jats:sub>\n                    )(C\n                    <jats:sub>6<\/jats:sub>\n                    F\n                    <jats:sub>5<\/jats:sub>\n                    )}). The behavior of these systems is shown to rely on the balance between the thermodynamics of H\n                    <jats:sub>2<\/jats:sub>\n                    activation and aggregation, and shows explicitly (but counter\u2010intuitively) how non\u2010covalent assembly can\n                    <jats:italic>impede<\/jats:italic>\n                    the activation of H\n                    <jats:sub>2<\/jats:sub>\n                    by FLPs.\n                  <\/jats:p>","DOI":"10.1002\/chem.71665","type":"journal-article","created":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T04:24:50Z","timestamp":1788841490000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Xanthene\u2010Based FLPs Featuring Perchloroarylborane Substitutents: Interplay of Noncovalent Aggregation and Dihydrogen Activation"],"prefix":"10.1002","author":[{"given":"Aisling F.","family":"Roper","sequence":"first","affiliation":[{"name":"Inorganic Chemistry Laboratory, Department of Chemistry University of Oxford  Oxford United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0786-5205","authenticated-orcid":false,"given":"Agamemnon E.","family":"Crumpton","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry Laboratory, Department of Chemistry University of Oxford  Oxford United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dermot","family":"O'Hare","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry Laboratory, Department of Chemistry University of Oxford  Oxford United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9998-9434","authenticated-orcid":false,"given":"Simon","family":"Aldridge","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry Laboratory, Department of Chemistry University of Oxford  Oxford United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,7]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"crossref","first-page":"325","DOI":"10.1021\/ja01254a031","article-title":"Studies in Stereochemistry. 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