{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T17:31:51Z","timestamp":1780507911650,"version":"3.54.1"},"reference-count":39,"publisher":"Wiley","issue":"20","license":[{"start":{"date-parts":[[2022,3,16]],"date-time":"2022-03-16T00:00:00Z","timestamp":1647388800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2022,3,16]],"date-time":"2022-03-16T00:00:00Z","timestamp":1647388800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/S036628\/1"],"award-info":[{"award-number":["EP\/S036628\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000761","name":"Imperial College London","doi-asserted-by":"publisher","award":["President's Scholarship"],"award-info":[{"award-number":["President's Scholarship"]}],"id":[{"id":"10.13039\/501100000761","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":[[2022,5,9]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Selective reactions that combine H\n                    <jats:sub>2<\/jats:sub>\n                    , CO and organic electrophiles (aldehyde, ketones, isocyanide) to form hydrogenated C\n                    <jats:sub>3<\/jats:sub>\n                    and C\n                    <jats:sub>4<\/jats:sub>\n                    carbon chains are reported. These reactions proceed by CO homologation mediated by [W(CO)\n                    <jats:sub>6<\/jats:sub>\n                    ] and an aluminum(I) reductant, followed by functionalization and hydrogenation of the chain ends. A combination of kinetics (rates, KIEs) and DFT calculations has been used to gain insight into a key step which involves hydrogenation of a metallocarbene intermediate. These findings expand the extremely small scope of systems that combine H\n                    <jats:sub>2<\/jats:sub>\n                    and CO to make well\u2010defined products with complete control over chain length and functionality.\n                  <\/jats:p>","DOI":"10.1002\/anie.202202241","type":"journal-article","created":{"date-parts":[[2022,2,28]],"date-time":"2022-02-28T05:16:30Z","timestamp":1646025390000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Functionalization and Hydrogenation of Carbon Chains Derived from CO**"],"prefix":"10.1002","volume":"61","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1430-1440","authenticated-orcid":false,"given":"Maria","family":"Batuecas","sequence":"first","affiliation":[{"name":"Department of Chemistry MSRH Imperial College London  82 Wood Lane, Shepherds Bush London W12 0BZ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Richard Y.","family":"Kong","sequence":"additional","affiliation":[{"name":"Department of Chemistry MSRH Imperial College London  82 Wood Lane, Shepherds Bush London W12 0BZ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andrew J. P.","family":"White","sequence":"additional","affiliation":[{"name":"Department of Chemistry MSRH Imperial College London  82 Wood Lane, Shepherds Bush London W12 0BZ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9339-9182","authenticated-orcid":false,"given":"Mark R.","family":"Crimmin","sequence":"additional","affiliation":[{"name":"Department of Chemistry MSRH Imperial College London  82 Wood Lane, Shepherds Bush London W12 0BZ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,3,16]]},"reference":[{"key":"e_1_2_3_1_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0926-860X(99)00160-X"},{"key":"e_1_2_3_2_1","first-page":"1","volume-title":"Kirk-Othmer Encyclopedia of Chemical Technology, Fischer\u2013Tropsch Process 1","author":"De Klerk A.","year":"2013"},{"key":"e_1_2_3_3_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1748201"},{"key":"e_1_2_3_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2010.08.019"},{"key":"e_1_2_3_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0DT01564D"},{"key":"e_1_2_3_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0360-0564(08)60443-5"},{"key":"e_1_2_3_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2017.02.007"},{"key":"e_1_2_3_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2004.05.037"},{"key":"e_1_2_3_9_1","doi-asserted-by":"publisher","DOI":"10.1007\/s11244-020-01248-5"},{"key":"e_1_2_3_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00450a065"},{"key":"e_1_2_3_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(92)83300-7"},{"key":"e_1_2_3_12_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1778"},{"key":"e_1_2_3_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b10108"},{"key":"e_1_2_3_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00017a030"},{"key":"e_1_2_3_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja406874k"},{"key":"e_1_2_3_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c10403"},{"key":"e_1_2_3_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c11482"},{"key":"e_1_2_3_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b09761"},{"key":"e_1_2_3_19_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC04940B"},{"key":"e_1_2_3_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198817031"},{"key":"e_1_2_3_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19881001216"},{"key":"e_1_2_3_21_1","unstructured":"To check if insertion could occur also into hydrogenated products reaction of3\u2009awith benzophenone was tested and no reactivity was observed suggesting that the reaction follows the sequence insertion\u2013hydrogenation."},{"key":"e_1_2_3_22_1","unstructured":"Although different geometries forInt-1can be proposed rotational barriers for H2ligand have been calculated to be low in energy for this molecule (\u0394G\u00b0298K=+3.2\u20136.8\u2005kcal\u2009mol\u22121and \u0394G\u2260298K=+0.7\u20134.5\u2005kcal\u2009mol\u22121) and are in agreement with previous results for related molecules (see Supporting Information)."},{"key":"e_1_2_3_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00237a011"},{"key":"e_1_2_3_24_1","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(84)85278-1"},{"key":"e_1_2_3_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00162a037"},{"key":"e_1_2_3_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar00077a004"},{"key":"e_1_2_3_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/C39860001185"},{"key":"e_1_2_3_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00447a065"},{"key":"e_1_2_3_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/om00126a031"},{"key":"e_1_2_3_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00236a044"},{"key":"e_1_2_3_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00264a009"},{"key":"e_1_2_3_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/om00093a017"},{"key":"e_1_2_3_33_1","unstructured":"Alternative mechanisms in whichInt-1undergoes CO dissociation to give a pentacoordinated dihydrogen intermediate or in which CO dissociation and H migration occur simultaneously fromInt-2have been discarded due to their high transition state energy:TS-2\u2009a \u0394G\u2260298K=+42.3\u2005kcal\u2009mol\u22121;TS-3\u2009b \u0394G\u2260298K=+44.0\u2005kcal\u2009mol\u22121(see Supporting Information)."},{"key":"e_1_2_3_34_1","unstructured":"An alternative plausible mechanism fromInt-5in which CO dissociation does not take place was calculated to present a similar energy (\u0394G\u2260298K=+35.9\u2005kcal\u2009mol\u22121) (see Supporting Information)."},{"key":"e_1_2_3_35_1","unstructured":"The energy span from4\u2009atoTS-6(\u0394G\u2260298K=+32.8\u2005kcal\u2009mol\u22121) is similar. These two steps are close in energy and either could be rate-limiting."},{"key":"e_1_2_3_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/om0303810"},{"key":"e_1_2_3_37_1","first-page":"1","volume-title":"Encyclopedia of Catalysis, Isotope Methods\u2014Homogeneous","author":"Bullock R M.","year":"2000"},{"key":"e_1_2_3_38_1","unstructured":"Deposition numbers\u20052130349 2130350 2130351 2129490 2129491 2129492contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202202241","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202202241","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202202241","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,3,18]],"date-time":"2026-03-18T06:46:15Z","timestamp":1773816375000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202202241"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,3,16]]},"references-count":39,"journal-issue":{"issue":"20","published-print":{"date-parts":[[2022,5,9]]}},"alternative-id":["10.1002\/anie.202202241"],"URL":"https:\/\/doi.org\/10.1002\/anie.202202241","archive":["Portico"],"relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv-2021-ndmfl","asserted-by":"object"}]},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,3,16]]},"assertion":[{"value":"2022-02-10","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2022-03-16","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202202241"}}