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Selective mono\u2010substitution of AlCl\n                    <jats:sub>3<\/jats:sub>\n                    with lithioarenes was achieved by introducing sterically demanding substituents\u2014\n                    <jats:italic>tert<\/jats:italic>\n                    \u2010butyl, ethyl, or PCy\n                    <jats:sub>2<\/jats:sub>\n                    \u2014at the 6\u2010position of the phenylene linker, effectively suppressing over\u2010substitution and enabling successful isolation of the target complexes. Single\u2010crystal X\u2010ray diffraction and NMR spectroscopic analyses confirmed the formation of a four\u2010membered P\u2013Al\u2013C\u2013C core structure. These complexes function as Al\/P\u2010based FLPs capable of activating simple carbonyl and imine compounds, including aliphatic ketones, prop\u20102\u2010ynoate esters, and\n                    <jats:italic>N<\/jats:italic>\n                    \u2010arylimines. The mechanism of carbonyl activation by these Al\/P FLPs was elucidated through density functional theory (DFT) calculations.\n                  <\/jats:p>","DOI":"10.1002\/chem.202502450","type":"journal-article","created":{"date-parts":[[2025,9,27]],"date-time":"2025-09-27T13:13:45Z","timestamp":1758978825000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["(2\u2010Phosphinophenyl)aluminum Dichloride Complexes as Intramolecular Al\/P Frustrated Lewis Pairs for Ketone, Ester, and Imine Activation"],"prefix":"10.1002","volume":"32","author":[{"given":"Yoshihiro","family":"Nishimoto","sequence":"first","affiliation":[{"name":"Department of Applied Chemistry, Graduate School of Engineering The University of Osaka 2\u20101 Yamadaoka Suita Osaka 565\u20130871 Japan"},{"name":"Innovative Catalysis Science Division Institute for Open and Transdisciplinary Research Initiatives (ICS\u2010OTRI) The University of Osaka 2\u20101 Yamadaoka Suita Osaka 565\u20130871 Japan"},{"name":"PRESTO Japan Science and Technology Agency (JST) Kawaguchi Saitama 332\u20130012 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hirotaka","family":"Okamoto","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, Graduate School of Engineering The University of Osaka 2\u20101 Yamadaoka Suita Osaka 565\u20130871 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Makoto","family":"Yasuda","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, Graduate School of Engineering The University of Osaka 2\u20101 Yamadaoka Suita Osaka 565\u20130871 Japan"},{"name":"Innovative Catalysis Science Division Institute for Open and Transdisciplinary Research Initiatives (ICS\u2010OTRI) The University of Osaka 2\u20101 Yamadaoka Suita Osaka 565\u20130871 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,9,27]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200903708"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4SC00395K"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar500375j"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b06794"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201409800"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2016.05.005"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CS00277K"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c10845"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202302332"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1098\/rsta.2017.0004"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CC05640B"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202405207"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.xcrp.2021.100595"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201706089"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201511048"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201901659"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201103600"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja9104792"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/om501036c"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0637494"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/om800101s"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/om4005884"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/om400645s"},{"key":"e_1_2_8_24_1","unstructured":"It is mentioned in ref. [19]that the selective synthesis of ArAlCl2 requires careful selection of the reaction conditions to avoid the generation of Ar2AlCl and Ar3Al via multiple substitutions."},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.202500174"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/cplu.202000239"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202101649"},{"key":"e_1_2_8_28_1","unstructured":"See details in the Supporting Information."},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic9515416"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic960486d"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19951280510"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201901791"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic800336f"},{"key":"e_1_2_8_34_1","unstructured":"Deposition Numbers 2470419 (forA\u20101) 2470361 (forA\u20102) 2470362 (forA\u20103) 2470427 (forA\u20101\u20221) 2470425 (forA\u20102\u20221) 2470428 (forA\u20103\u20221) 2470367 (forC\u20102) 2470451 (forC\u20103) 2470420 (forD\u20102) 2470744 (forD\u20103) 2470418 (forE\u20102) and 2470368 (forE\u20103) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service."},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1039\/b801115j"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(99)00053-4"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC00291A"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00096a015"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CC02173B"},{"key":"e_1_2_8_40_1","unstructured":"We performed DFT calculations for the activation of ester4with the AltBu2complexA\u20104 corresponding toA\u20102 to demonstrate the importance of the high Lewis acidity of the AlCl2group in enabling the activation of less reactive carbonyl compounds (see pp. 40\u201342 in the Supporting Information)."},{"key":"e_1_2_8_41_1","unstructured":"We confirmed that like the other reported Al\/P FLPs complexes A also activate aldehydes and isocyanates. On the other hand ethynylarenes were not activated most likely because ethynylarenes cannot displace the phosphino\u2010substituent from the aluminum center and coordinate to it owing to the weak coordinating ability of the C\u2013C triple bond."},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202007595"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-2002-33339"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2004.05.044"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo501965y"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.3987\/COM-08-S(N)125"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202502450","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.202502450","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202502450","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202502450","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T23:08:35Z","timestamp":1785452915000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202502450"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,9,27]]},"references-count":46,"journal-issue":{"issue":"28","published-print":{"date-parts":[[2026,7,25]]}},"alternative-id":["10.1002\/chem.202502450"],"URL":"https:\/\/doi.org\/10.1002\/chem.202502450","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,9,27]]},"assertion":[{"value":"2025-08-01","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-09-22","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-09-27","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e02450"}}