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However, a comprehensive understanding of its mechanism has only recently begun to emerge. X\u2010ray spectroscopy, because of its high selectivity and sensitivity, is the ideal tool for distinguishing between an ensemble of competing pathways. With this aim in mind, we investigated the concerted mechanism of the addition of methylmagnesium chloride (CH<jats:sub>3<\/jats:sub>MgCl) to acetone in tetrahydrofuran by simulating the X\u2010ray spectra of different molecules in solution. We used electronic structure methods to calculate the X\u2010ray absorption spectra at the Mg K\u2010 and L<jats:sub>1<\/jats:sub>\u2010edges and the X\u2010ray photoelectron spectra at the Mg K\u2010edge for different organomagnesium species, which coexist in solution due to the Schlenk equilibrium. The simulated spectra show that individual species can be distinguished throughout the different stages of the reaction. Each species has a distinct spectral feature which can be used as a fingerprint in solution. The absorption and photoelectron spectra consistently show a blue shift as the reaction progressed from reagents to products.<\/jats:p>","DOI":"10.1002\/chem.202402099","type":"journal-article","created":{"date-parts":[[2024,9,19]],"date-time":"2024-09-19T08:18:28Z","timestamp":1726733908000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Distinguishing Organomagnesium Species in the Grignard Addition to Ketones with X\u2010Ray Spectroscopy"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8852-1016","authenticated-orcid":false,"given":"Lorenzo","family":"Restaino","sequence":"first","affiliation":[{"name":"Department of Physics Stockholm University Albanova University Centre  SE-106 91 Stockholm Sweden"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6343-6256","authenticated-orcid":false,"given":"Riccardo","family":"Mincigrucci","sequence":"additional","affiliation":[{"name":"Elettra Sincrotrone Trieste SCpA  Strada Statale 14 - km 163,5 in AREA Science Park 34149 Basovizza Trieste Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2288-2548","authenticated-orcid":false,"given":"Markus","family":"Kowalewski","sequence":"additional","affiliation":[{"name":"Department of Physics Stockholm University Albanova University Centre  SE-106 91 Stockholm Sweden"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,11,7]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"M.\u2005Victor Grignard Sur quelques nouvelles combinaisons organom\u00e9talliques du magn\u00e9sium et leur application \u00e0 des synth\u00e8ses daalcools et d'hydrocarbures Ph.D. thesis1901."},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(02)01165-8"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19290620422"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/om900088z"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp035653r"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcb.7b02716"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1201\/b16932"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00468a022"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.3891\/acta.chem.scand.42b-0685"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b11829"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01063a026"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00734a030"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00981a009"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198004871"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100546a025"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/j19710000184"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198405341"},{"key":"e_1_2_8_18_1","doi-asserted-by":"crossref","unstructured":"P.\u2005R. 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