{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T16:20:35Z","timestamp":1791476435936,"version":"4.3.4"},"reference-count":57,"publisher":"Wiley","issue":"46","license":[{"start":{"date-parts":[[2025,9,20]],"date-time":"2025-09-20T00:00:00Z","timestamp":1758326400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2025,9,20]],"date-time":"2025-09-20T00:00:00Z","timestamp":1758326400000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/100011264","name":"FP7 People: Marie-Curie Actions","doi-asserted-by":"publisher","award":["PIEF\u2010GA\u20102013\u2010626441"],"award-info":[{"award-number":["PIEF\u2010GA\u20102013\u2010626441"]}],"id":[{"id":"10.13039\/100011264","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/K014714\/1"],"award-info":[{"award-number":["EP\/K014714\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000275","name":"Leverhulme Trust","doi-asserted-by":"publisher","award":["RP\u20102018\u2010246"],"award-info":[{"award-number":["RP\u20102018\u2010246"]}],"id":[{"id":"10.13039\/501100000275","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2025,11,10]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    The hydroboration of aldehydes and ketones by pinacolborane (HBpin) catalysed by (Nacnac)\n                    <jats:sup>Dipp<\/jats:sup>\n                    Al(OTf)H ((Nacnac)\n                    <jats:sup>Dipp<\/jats:sup>\n                    \u00a0=\u00a0HC(MeCDippN)\n                    <jats:sub>2<\/jats:sub>\n                    ; Dipp\u00a0=\u00a0C\n                    <jats:sub>6<\/jats:sub>\n                    H\n                    <jats:sub>3<\/jats:sub>\n                    <jats:italic>\n                      <jats:sup>i<\/jats:sup>\n                    <\/jats:italic>\n                    Pr\n                    <jats:sub>2<\/jats:sub>\n                    \u20102,6; Tf\u00a0=\u00a0SO\n                    <jats:sub>2<\/jats:sub>\n                    CF\n                    <jats:sub>3<\/jats:sub>\n                    ) was first reported in 2015. This study represented a landmark in main group catalysis, and advanced a widely\u2010accepted and oft\u2010cited mechanistic paradigm. However, in contradiction of that study, we show here that: i) the mechanism proposed, involving turnover via Al\u2500O\/B\u2500H metathesis at the intermediate (Nacnac)\n                    <jats:sup>Dipp<\/jats:sup>\n                    Al(OTf)(OCH\n                    <jats:sub>2<\/jats:sub>\n                    Ph), does not occur; ii) when using pre\u2010purified HBpin, the hydroboration reaction with acetophenone \u2018catalysed\u2019 by (Nacnac)\n                    <jats:sup>Dipp<\/jats:sup>\n                    Al(OTf)H (reportedly giving 51% conversion over 6\u00a0h at 2\u00a0mol% loading), actually shows no conversion; and iii) the active species in catalysis is a BH\n                    <jats:sub>3<\/jats:sub>\n                    adduct derived either from the use of impure HBpin, or from the degradation of HBpin by the action of aluminium species present in the reaction mixture. More broadly, our study i) calls into question the nature of the true catalyst species in reports of carbonyl hydroboration by aluminium complexes (since Al\u2500O\/B\u2500H metathesis proceeds spontaneously in the\n                    <jats:italic>reverse<\/jats:italic>\n                    direction to that necessitated catalytically); and ii) presents further evidence that the hydroboration of benzaldehyde by HBpin is not a good catalytic probe, given the significant rate of the uncatalysed background reaction.\n                  <\/jats:p>","DOI":"10.1002\/anie.202517007","type":"journal-article","created":{"date-parts":[[2025,9,20]],"date-time":"2025-09-20T07:07:51Z","timestamp":1758352071000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["On the Viability of Carbonyl Hydroboration Catalysed by Aluminium Hydrides"],"prefix":"10.1002","volume":"64","author":[{"given":"Alexa","family":"Caise","sequence":"first","affiliation":[{"name":"Inorganic Chemistry Laboratory Department of Chemistry University of Oxford  South Parks Road Oxford OX1 3QR UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Barnab\u00e9","family":"Berger","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry Laboratory Department of Chemistry University of Oxford  South Parks Road Oxford OX1 3QR UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aidan","family":"Murray","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry Laboratory Department of Chemistry University of Oxford  South Parks Road Oxford OX1 3QR UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Eugene","family":"Kolychev","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry Laboratory Department of Chemistry University of Oxford  South Parks Road Oxford OX1 3QR UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jamie","family":"Hicks","sequence":"additional","affiliation":[{"name":"Research School of Chemistry The Australian National University  Building 137 Sullivans Creek Road Canberra ACT 2601 Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"M.","family":"\u00c1ngeles Fuentes","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Center for Research in Sustainable Chemistry (CIQSO) University of Huelva  Huelva 21007 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Job J. C.","family":"Struijs","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry Laboratory Department of Chemistry University of Oxford  South Parks Road Oxford OX1 3QR UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jose M.","family":"Goicoechea","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indiana University  800 E. Kirkwood Ave Bloomington IN 47405 USA"}],"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  South Parks Road Oxford OX1 3QR UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,9,20]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1007\/1-4020-2000-7"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527699087"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00076"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201409800"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature08634"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201800963"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c12816"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja053247a"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b00428"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc30565h"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/C3SC52793J"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC05708F"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5SC03114A"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201601623"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7DT00556C"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201408760"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20001002)6:19<3586::AID-CHEM3586>3.0.CO;2-S"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja5006477"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC06805G"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6DT04893E"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201803804"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201500570"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202004408"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201802603"},{"key":"e_1_2_9_25_1","first-page":"1","volume-title":"The Chemistry of the Group 13 Metals Aluminium, Gallium, Indium and Thallium: Chemical Patterns and Peculiarities","author":"Downs A. J.","year":"2011"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201503304"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b00032"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2DT00785A"},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2017.03.017"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.7b02460"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201800045"},{"key":"e_1_2_9_32_1","doi-asserted-by":"publisher","DOI":"10.1039\/9781788012775-00261"},{"key":"e_1_2_9_33_1","first-page":"335","volume-title":"Aluminum Complexes in Organic Synthesis in Comprehensive Organometallic Chemistry IV: Volume 1\u201015","author":"Vidovi\u0107 D.","year":"2022"},{"key":"e_1_2_9_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.1c00278"},{"key":"e_1_2_9_35_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.202100929"},{"key":"e_1_2_9_36_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1DT03703J"},{"key":"e_1_2_9_37_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7RA06526D"},{"key":"e_1_2_9_38_1","unstructured":"In our hands the gallium analogue of3\u2010OTf i.e. (Nacnac)DippGa(OTf)H does not insert benzaldehyde into the Ga\u2013H bond to give (Nacnac)DippGa(OTf)OCH2Ph. A. Caise D.Phil. thesis \u03b2\u2010Diketiminate complexes of group 13 elements and their use in small molecule activation and catalysis University of Oxford September 2018.https:\/\/ora.ox.ac.uk\/objects\/uuid:c9d953ee\u20107ffd\u201041b6\u2010aaca\u2010d5d67162c1e1. Retrieved 26 July 2025."},{"key":"e_1_2_9_39_1","unstructured":"The results of DFT calculations are consistent with the experimental observations outlined in Scheme 3 (see Figure S29). Thermodynamically the reaction of4\u2010OTf with HBpin to give3\u2010OTf and PhCH2OBpin is endergonic by \u0394G\u00a0=\u00a0+25.5\u00a0kJ mol\u20101 with the activation barriers associated with the forward and reverse reactions being +79.9 and 54.4\u00a0kJ mol\u22121 respectively."},{"key":"e_1_2_9_40_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2006.824"},{"key":"e_1_2_9_41_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8GC00042E"},{"key":"e_1_2_9_42_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9NJ02722J"},{"key":"e_1_2_9_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.0c04051"},{"key":"e_1_2_9_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.4c03591"},{"key":"e_1_2_9_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo201142g"},{"key":"e_1_2_9_46_1","unstructured":"The same signal at\u03b4B\u00a0=\u00a0\u221213.6\u00a0ppm is obtained on addition of Me2S\u00b7BH3to purified HBpin suggesting a potential adduct of the form: ."},{"key":"e_1_2_9_47_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201406585"},{"key":"e_1_2_9_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.3c03194"},{"key":"e_1_2_9_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.1c00619"},{"key":"e_1_2_9_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.0c01168"},{"key":"e_1_2_9_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.0c00086"},{"key":"e_1_2_9_52_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC09111D"},{"key":"e_1_2_9_53_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9DT00535H"},{"key":"e_1_2_9_54_1","doi-asserted-by":"publisher","DOI":"10.1039\/c1cc14689k"},{"key":"e_1_2_9_55_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00062a048"},{"key":"e_1_2_9_56_1","unstructured":"Deposition numbers 2445257 ((Nacnac)DippGa(OTf)H) 2445258 (compound4\u2010Et) 2445259 (compound4\u2010Cl) 2445260 ((Nacnac)DippGa(H)(OCH2Ph)) 2445261 (compounds4\u2010OTf) and 2445262 ((Nacnac)DippAl(BH4)2) 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 (http:\/\/www.ccdc.cam.ac.uk\/structures)."},{"key":"e_1_2_9_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic0517826"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202517007","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202517007","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202517007","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,4,9]],"date-time":"2026-04-09T14:27:04Z","timestamp":1775744824000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202517007"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,9,20]]},"references-count":57,"journal-issue":{"issue":"46","published-print":{"date-parts":[[2025,11,10]]}},"alternative-id":["10.1002\/anie.202517007"],"URL":"https:\/\/doi.org\/10.1002\/anie.202517007","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,9,20]]},"assertion":[{"value":"2025-08-03","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-09-08","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-09-20","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202517007"}}