{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,9]],"date-time":"2026-03-09T10:03:46Z","timestamp":1773050626631,"version":"3.50.1"},"reference-count":43,"publisher":"Wiley","issue":"42","license":[{"start":{"date-parts":[[2024,7,9]],"date-time":"2024-07-09T00:00:00Z","timestamp":1720483200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["21973113"],"award-info":[{"award-number":["21973113"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22373118"],"award-info":[{"award-number":["22373118"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100021171","name":"Basic and Applied Basic Research Foundation of Guangdong Province","doi-asserted-by":"publisher","award":["2024B1515040025"],"award-info":[{"award-number":["2024B1515040025"]}],"id":[{"id":"10.13039\/501100021171","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2024,7,25]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The Guerbet reaction is important for the synthesis of longer\u2010chain monoalcohols like isobutanol through catalytic transfer hydrogenation from short\u2010chain methanol and ethanol. However, the mechanism becomes complicated, especially considering the variations in the different metal\u2010ligand cooperation (MLC) catalysts used. In order to further understand the Guerbet reaction, DFT studies were performed to figure out the detailed mechanism initiated by the unique Mn\u2010PCP MLC Catalyst. Our results suggest that even with the assistance of the carbanion site of the PCP ligand, the direct substitution mechanism is less favored than the condensation\u2010reduction mechanism. The key step of the reaction is the final reduction of the carbonyl, in which the 1,4\u2010reduction of the unsaturated aldehyde is prior to the 3,4\u2010reduction or 1,2\u2010reduction due to the stronger interaction between the catalyst and the substrate. It is found that the production of isobutanol is preferred over <jats:italic>n<\/jats:italic>\u2010butanol because of the lower total free energy barrier and lower relative free energy of the product. Finally, by changing the electronic effect of the carbanion site of the catalyst, we found that the relation between the electronic effect and the highest free energy span was not monotonous and a point with optimal electronic effect exists numerically.<\/jats:p>","DOI":"10.1002\/chem.202303861","type":"journal-article","created":{"date-parts":[[2024,5,16]],"date-time":"2024-05-16T01:44:27Z","timestamp":1715823867000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["The Mechanism of Guerbet Reaction by Metal Ligand Cooperation Catalyst Mn\u2010PCP"],"prefix":"10.1002","volume":"30","author":[{"given":"Ruzhao","family":"Chen","sequence":"first","affiliation":[{"name":"School of Chemistry School of Materials Science and Engineering PCFM Lab the Key Laboratory of Low-carbon Chemistry &amp; Energy Conservation of Guangdong Province Sun Yat-sen University  Guangzhou 510275 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xiaoyu","family":"Zhou","sequence":"additional","affiliation":[{"name":"School of Pharmaceutical and Chemical Engineering Taizhou University  Taizhou 317700 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Fuyi","family":"Yang","sequence":"additional","affiliation":[{"name":"School of Chemistry School of Materials Science and Engineering PCFM Lab the Key Laboratory of Low-carbon Chemistry &amp; Energy Conservation of Guangdong Province Sun Yat-sen University  Guangzhou 510275 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Cunyuan","family":"Zhao","sequence":"additional","affiliation":[{"name":"School of Chemistry School of Materials Science and Engineering PCFM Lab the Key Laboratory of Low-carbon Chemistry &amp; Energy Conservation of Guangdong Province Sun Yat-sen University  Guangzhou 510275 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9064-8051","authenticated-orcid":false,"given":"Zhuofeng","family":"Ke","sequence":"additional","affiliation":[{"name":"School of Chemistry School of Materials Science and Engineering PCFM Lab the Key Laboratory of Low-carbon Chemistry &amp; Energy Conservation of Guangdong Province Sun Yat-sen University  Guangzhou 510275 China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,7,9]]},"reference":[{"key":"e_1_2_10_1_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1114736"},{"key":"e_1_2_10_2_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1137013"},{"key":"e_1_2_10_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/biot.200700168"},{"key":"e_1_2_10_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201303723"},{"key":"e_1_2_10_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC09913G"},{"key":"e_1_2_10_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b01327"},{"key":"e_1_2_10_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b05433"},{"key":"e_1_2_10_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4GC00510D"},{"key":"e_1_2_10_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b05939"},{"key":"e_1_2_10_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.7b03653"},{"key":"e_1_2_10_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2016.08.024"},{"key":"e_1_2_10_12_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcata.2021.118272"},{"key":"e_1_2_10_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1872-2067(20)63541-0"},{"key":"e_1_2_10_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202200539"},{"key":"e_1_2_10_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC05860D"},{"key":"e_1_2_10_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4GC00219A"},{"key":"e_1_2_10_17_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC01599A"},{"key":"e_1_2_10_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.1c00313"},{"key":"e_1_2_10_19_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7DT01022B"},{"key":"e_1_2_10_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.201802689"},{"key":"e_1_2_10_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00509F"},{"key":"e_1_2_10_22_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5GC02963E"},{"key":"e_1_2_10_23_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1381-1169(03)00042-6"},{"key":"e_1_2_10_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/om200089m"},{"key":"e_1_2_10_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp2046728"},{"key":"e_1_2_10_26_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CY00501C"},{"key":"e_1_2_10_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CY00243J"},{"key":"e_1_2_10_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.0c04616"},{"key":"e_1_2_10_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.0c00588"},{"key":"e_1_2_10_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC07713H"},{"key":"e_1_2_10_31_1","unstructured":"Gaussian 16 Rev. A.03; Frisch M.\u2005J.; Trucks G.\u2005W.; Schlegel H.\u2005B.; Scuseria G.\u2005E.; Robb M.\u2005A.; Cheeseman J.\u2005R.; Scalmani G.; Barone V.; Petersson G.\u2005A.; Nakatsuji H.; Li X.; Caricato M.; Marenich A.\u2005V.; Bloino J.; Janesko B.\u2005G.; Gomperts R.; Mennucci B.; Hratchian H.\u2005P.; Ortiz J.\u2005V.; Izmaylov A.\u2005F.; Sonnenberg J.\u2005L.; Williams; Ding F.; Lipparini F.; Egidi F.; Goings J.; Peng B.; Petrone A.; Henderson T.; Ranasinghe D.; Zakrzewski V.\u2005G.; Gao J.; Rega N.; Zheng G.; Liang W.; Hada M.; Ehara M.; Toyota K.; Fukuda R.; Hasegawa J.; Ishida M.; Nakajima T.; Honda Y.; Kitao O.; Nakai H.; Vreven T.; Throssell K.; Montgomery Jr. J.\u2005A.; Peralta J.\u2005E.; Ogliaro F.; Bearpark M.\u2005J.; Heyd J.\u2005J.; Brothers E.\u2005N.; Kudin K.\u2005N.; Staroverov V.\u2005N.; Keith T.\u2005A.; Kobayashi R.; Normand J.; Raghavachari K.; Rendell A.\u2005P.; Burant J.\u2005C.; Iyengar S.\u2005S.; Tomasi J.; Cossi M.; Millam J.\u2005M.; Klene M.; Adamo C.; Cammi R.; Ochterski J.\u2005W.; Martin R.\u2005L.; Morokuma K.; Farkas O.; Foresman J.\u2005B.; Fox D.\u2005J.: 2016."},{"key":"e_1_2_10_32_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00214-007-0401-8"},{"key":"e_1_2_10_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/b515623h"},{"key":"e_1_2_10_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp810292n"},{"key":"e_1_2_10_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jcim.9b00725"},{"key":"e_1_2_10_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar00072a001"},{"key":"e_1_2_10_37_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.22885"},{"key":"e_1_2_10_38_1","unstructured":"C.\u2005Y.\u2005C. Legault 1.0b Universitede Sherbrooke: Qu\u00e9bec C. Montreal 2009;http:\/\/www.cylview.org."},{"key":"e_1_2_10_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.7b00355"},{"key":"e_1_2_10_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp980229p"},{"key":"e_1_2_10_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.7b11580"},{"key":"e_1_2_10_42_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.2747247"},{"key":"e_1_2_10_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar1000956"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202303861","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T14:41:05Z","timestamp":1760280065000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202303861"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,7,9]]},"references-count":43,"journal-issue":{"issue":"42","published-print":{"date-parts":[[2024,7,25]]}},"alternative-id":["10.1002\/chem.202303861"],"URL":"https:\/\/doi.org\/10.1002\/chem.202303861","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,7,9]]},"assertion":[{"value":"2023-11-20","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-07-09","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202303861"}}