{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,26]],"date-time":"2026-02-26T15:14:42Z","timestamp":1772118882951,"version":"3.50.1"},"reference-count":53,"publisher":"Wiley","issue":"15","license":[{"start":{"date-parts":[[2025,5,1]],"date-time":"2025-05-01T00:00:00Z","timestamp":1746057600000},"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":["22206195"],"award-info":[{"award-number":["22206195"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["analyticalsciencejournals.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Rapid Comm Mass Spectrometry"],"published-print":{"date-parts":[[2025,8,15]]},"abstract":"ABSTRACT<\/jats:title>\n \n Rationale<\/jats:title>\n The lanthanide hydrocarbyl complexes often exhibit exceptional performance in organic synthesis, catalytic process, and small molecule activation, and they generally exhibit several valuable differences in reactivity which can be influenced by the metal center and its oxidation state. Decarboxylation of metal carboxylate precursor is a powerful means to obtain multitudinous organometallic complexes which are well suited for gas\u2010phase investigation by employing electrospray ionization mass spectrometry (ESI\u2010MS) experiments in combination with density functional theory (DFT) calculations.<\/jats:p>\n <\/jats:sec>\n \n Methods<\/jats:title>\n \n The (CH\n 3<\/jats:sub>\n CO\n 2<\/jats:sub>\n )LnCl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n and (CH\n 3<\/jats:sub>\n CO\n 2<\/jats:sub>\n )\n 2<\/jats:sub>\n LnCl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n (Ln\u2009=\u2009Sm, Eu, and Yb) precursor anions were produced in the gas phase via ESI of LnCl\n 3<\/jats:sub>\n and CH\n 3<\/jats:sub>\n CO\n 2<\/jats:sub>\n Na mixtures in methanol. Collision\u2010induced dissociation (CID) technique was employed to obtain (CH\n 3<\/jats:sub>\n )Ln\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n and (CH\n 3<\/jats:sub>\n )Ln\n II<\/jats:sup>\n Cl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n via fragmentation reactions of lanthanide acetate chloride anions. Activation of water molecule by (CH\n 3<\/jats:sub>\n )Ln\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n or (CH\n 3<\/jats:sub>\n )Ln\n II<\/jats:sup>\n Cl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n via CH\n 4<\/jats:sub>\n or H\n 2<\/jats:sub>\n release was investigated by ion\u2010molecule reaction (IMR) experiments. With the support of DFT calculations, the influences of lanthanide center and its oxidation state were also explored.\n <\/jats:p>\n <\/jats:sec>\n \n Results<\/jats:title>\n \n (CH\n 3<\/jats:sub>\n )Ln\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n was generated via decarboxylation of (CH\n 3<\/jats:sub>\n CO\n 2<\/jats:sub>\n )LnCl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n (Ln\u2009=\u2009Sm, Eu, and Yb) upon CID, while (CH\n 3<\/jats:sub>\n CO\n 2<\/jats:sub>\n )\n 2<\/jats:sub>\n LnCl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n underwent consecutive two\u2010step CO\n 2<\/jats:sub>\n \/CH\n 3<\/jats:sub>\n or one\u2010step CH\n 3<\/jats:sub>\n CO\n 2<\/jats:sub>\n \u00b7and CO\n 2<\/jats:sub>\n losses to give (CH\n 3<\/jats:sub>\n )Ln\n II<\/jats:sup>\n Cl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n . All three (CH\n 3<\/jats:sub>\n )Ln\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n anions spontaneously reacted with H\n 2<\/jats:sub>\n O to form Ln (OH)Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n accompanied by methane release, and the reaction extent is generally following as (CH\n 3<\/jats:sub>\n )Sm\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n \u2009>\u2009(CH\n 3<\/jats:sub>\n )Eu\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n \u2009>\u2009(CH\n 3<\/jats:sub>\n )Yb\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n . For (CH\n 3<\/jats:sub>\n )Eu\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n with H\n 2<\/jats:sub>\n O, there was minor (CH\n 3<\/jats:sub>\n O)EuCl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n produced through hydrogen loss reaction as well. Three (CH\n 3<\/jats:sub>\n )Ln\n II<\/jats:sup>\n Cl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n anions reacted much more quickly than (CH\n 3<\/jats:sub>\n )Ln\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n with H\n 2<\/jats:sub>\n O via CH\n 4<\/jats:sub>\n loss, and the reactivity enhancement extent is following as Yb\u2009>\u2009Eu\u2009>\u2009Sm, which agrees well with Ln\u2010C bond elongation trend from (CH\n 3<\/jats:sub>\n )Ln\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n to (CH\n 3<\/jats:sub>\n )Ln\n II<\/jats:sup>\n Cl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n . Moreover, (CH\n 3<\/jats:sub>\n )Sm\n II<\/jats:sup>\n Cl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n and (CH\n 3<\/jats:sub>\n )Yb\n II<\/jats:sup>\n Cl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n rather than (CH\n 3<\/jats:sub>\n )Eu\n II<\/jats:sup>\n Cl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n underwent H\n 2<\/jats:sub>\n loss reaction with H\n 2<\/jats:sub>\n O, which is on the contrary with the cases of (CH\n 3<\/jats:sub>\n )Ln\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n .\n <\/jats:p>\n <\/jats:sec>\n \n Conclusion<\/jats:title>\n \n The reactivity of the methyllanthanide chloride complexes towards water is significantly influenced by the lanthanide center and its oxidation state. In general, the methyllanthanide (II) chloride complexes (CH\n 3<\/jats:sub>\n )Ln\n II<\/jats:sup>\n Cl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n is much more reactive than the methyllanthanide (III) chloride complexes (CH\n 3<\/jats:sub>\n )Ln\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n . Besides, the reactivity of (CH\n 3<\/jats:sub>\n )Ln\n III<\/jats:sup>\n Cl\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n is following as Sm\u2009>\u2009Eu\u2009>\u2009Yb, while that of (CH\n 3<\/jats:sub>\n )Ln\n II<\/jats:sup>\n Cl\n 2<\/jats:sub>\n \u2212<\/jats:sup>\n is Eu\u2009>\u2009Sm\u2009\u2248\u2009Yb.\n <\/jats:p>\n <\/jats:sec>","DOI":"10.1002\/rcm.10054","type":"journal-article","created":{"date-parts":[[2025,5,1]],"date-time":"2025-05-01T10:35:04Z","timestamp":1746095704000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Water Activation by Methyllanthanides: Hydrogen Versus Methane Evolution"],"prefix":"10.1002","volume":"39","author":[{"given":"Songpeng","family":"Wan","sequence":"first","affiliation":[{"name":"National Key Laboratory of Thorium Energy Shanghai Institute of Applied Physics, Chinese Academy of Sciences Shanghai China"},{"name":"University of Chinese Academy of Sciences Beijing China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8847-1047","authenticated-orcid":false,"given":"Yu","family":"Gong","sequence":"additional","affiliation":[{"name":"National Key Laboratory of Thorium Energy Shanghai Institute of Applied Physics, Chinese Academy of Sciences Shanghai China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2730-0949","authenticated-orcid":false,"given":"Xiuting","family":"Chen","sequence":"additional","affiliation":[{"name":"National Key Laboratory of Thorium Energy Shanghai Institute of Applied Physics, Chinese Academy of Sciences Shanghai China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,5]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2019.07.002"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2021.213830"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199524661"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr010315c"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202200202"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/c29700000244"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1201\/9781315380476"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00191a046"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/a901434i"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00098a063"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00105a065"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022\u2010328x(01)01477\u20102"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc34630c"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3cc45611k"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo501797w"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200901927"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201704383"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic0109492"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00041a024"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja045064e"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/om050296n"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/d1cc00965f"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar500377u"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/om900053c"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/om3011917"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201901360"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/om500493w"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja048476w"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.6b00079"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1039\/d1cp03092b"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/jasms.2c00236"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/d1cc06925j"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1039\/d2cc02057b"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010024\u201051167\u20102"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/rcm.9512"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/jasms.4c00001"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/jms.4430"},{"key":"e_1_2_8_39_1","volume-title":"Gaussian_09, Revision A.01","author":"Frisch M. 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