{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,6]],"date-time":"2026-03-06T02:39:30Z","timestamp":1772764770942,"version":"3.50.1"},"reference-count":27,"publisher":"MDPI AG","issue":"4","license":[{"start":{"date-parts":[[2024,2,16]],"date-time":"2024-02-16T00:00:00Z","timestamp":1708041600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"FCT","doi-asserted-by":"publisher","award":["UIDB\/00100\/2020"],"award-info":[{"award-number":["UIDB\/00100\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"FCT","doi-asserted-by":"publisher","award":["UIDP\/00100\/2020"],"award-info":[{"award-number":["UIDP\/00100\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"FCT","doi-asserted-by":"publisher","award":["LA\/P\/0056\/2020"],"award-info":[{"award-number":["LA\/P\/0056\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>C-scorpionate metal complexes, specifically, [NiCl2(tpm)]\u00b73H2O, [CoCl2(tpm)]\u00b73H2O and [PdCl2(tpm)] [tpm = hydrotris(1H-pyrazol-1-yl)methane], were effective in the N-formylation and N-methylation of amines using carbon dioxide, as carbon source, in the presence of sodium borohydride. Various parameters were studied, including reaction time, temperature, solvent volume, presence of additives, and catalyst amount. These parameters were found to have a significant impact on the selectivity of the product. [NiCl2(tpm)]\u00b73H2O exhibited good conversion at 80 \u00b0C, but its selectivity towards formamide decreased with prolonged reaction time. Increasing the amount of [NiCl2(tpm)]\u00b73H2O, the selectivity changed. [PdCl2(tpm)] showed different selectivity compared to [NiCl2(tpm)]\u00b73H2O, while [CoCl2(tpm)]\u00b73H2O presented poor results. Monitoring the reaction course by 1H NMR revealed the presence of an intermediate species that influenced product formation. These results highlight the versatility and catalytic potential of C-scorpionate metal complexes in the N-formylation\/N-methylation of amines in the catalytic system (NaBH4\/MeCN\/CO2).<\/jats:p>","DOI":"10.3390\/molecules29040870","type":"journal-article","created":{"date-parts":[[2024,2,16]],"date-time":"2024-02-16T03:37:27Z","timestamp":1708054647000},"page":"870","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["CO2-Driven N-Formylation\/N-Methylation of Amines Using C-Scorpionate Metal Complexes"],"prefix":"10.3390","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5501-7913","authenticated-orcid":false,"given":"In\u00eas A. S.","family":"Matias","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Departamento de Engenahria Qu\u00edmica, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4388-2109","authenticated-orcid":false,"given":"Anna M.","family":"Trzeciak","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, University of Wroc\u0142aw, 14 F. Joliot-Curie, 50-383 Wroc\u0142aw, Poland"}]},{"given":"Paulina","family":"P\u0105chalska","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, University of Wroc\u0142aw, 14 F. Joliot-Curie, 50-383 Wroc\u0142aw, Poland"}]},{"given":"Ana P. C.","family":"Ribeiro","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Departamento de Engenahria Qu\u00edmica, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5403-9352","authenticated-orcid":false,"given":"Lu\u00edsa M. D. R. S.","family":"Martins","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Departamento de Engenahria Qu\u00edmica, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2024,2,16]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"17612","DOI":"10.1021\/acs.iecr.0c02218","article-title":"Dual-Function Materials for CO2 Capture and Conversion: A Review","volume":"59","author":"Omodolor","year":"2020","journal-title":"Ind. Eng. Chem. 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