{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,21]],"date-time":"2026-09-21T03:20:34Z","timestamp":1789960834978,"version":"4.0.1"},"reference-count":55,"publisher":"Wiley","issue":"15","license":[{"start":{"date-parts":[[2022,2,18]],"date-time":"2022-02-18T00:00:00Z","timestamp":1645142400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["HA 3218\/11-1"],"award-info":[{"award-number":["HA 3218\/11-1"]}],"id":[{"id":"10.13039\/501100001659","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":[[2022,4,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>In order to isolate a monometallic Mg radical, the precursor (Am)MgI\u22c5(CAAC) (<jats:bold>1<\/jats:bold>) was prepared (Am=<jats:italic>t<\/jats:italic>BuC(N\u2010DIPP)<jats:sub>2<\/jats:sub>, DIPP=2,6\u2010diisopropylphenyl, CAAC=cyclic (alkyl)(amino)carbene). Reduction of a solution of <jats:bold>1<\/jats:bold> in toluene with the reducing agent K\/KI led to formation of a deep purple complex that rapidly decomposed. Ball\u2010milling of <jats:bold>1<\/jats:bold> with K\/KI gave the low\u2010valent Mg<jats:sup>I<\/jats:sup> complex (Am)Mg\u22c5(CAAC) (<jats:bold>2<\/jats:bold>) which after rapid extraction with pentane and crystallization was isolated in 15\u2009% yield. Although a benzene solution of <jats:bold>2<\/jats:bold> decomposes rapidly to give Mg(Am)<jats:sub>2<\/jats:sub> (<jats:bold>3<\/jats:bold>) and unidentified products, the radical is stable in the solid state. Its crystal structure shows planar trigonal coordination at Mg. The extremely short Mg\u2212C distance of 2.056(2)\u2005\u00c5 indicates strong Mg\u2212CAAC bonding. Calculations and EPR measurements show that most of the spin density is in a \u03c0* orbital located at the C\u2212N bond in CAAC, leading to significant C\u2212N bond elongation. This is supported by calculated NPA charges in <jats:bold>2<\/jats:bold>: Mg +1.73, CAAC \u22120.82. Similar metal\u2010to\u2010CAAC charge transfer was calculated for M<jats:sup>0<\/jats:sup>(CAAC)<jats:sub>2<\/jats:sub> and [M<jats:sup>I<\/jats:sup>(CAAC)<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup>] (M=Be, Mg, Ca) complexes in which the metal charges range from +1.50 to +1.70. Although the spin density of the radical is mainly located at the CAAC ligand, complex <jats:bold>2<\/jats:bold> reacts as a low\u2010valent Mg<jats:sup>I<\/jats:sup> complex: reaction with a I<jats:sub>2<\/jats:sub> solution in toluene gave (Am)MgI\u22c5(CAAC) (<jats:bold>1<\/jats:bold>) as the major product.<\/jats:p>","DOI":"10.1002\/anie.202200511","type":"journal-article","created":{"date-parts":[[2022,2,2]],"date-time":"2022-02-02T17:33:53Z","timestamp":1643823233000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":65,"title":["Access to a Labile Monomeric Magnesium Radical by Ball\u2010Milling"],"prefix":"10.1002","volume":"61","author":[{"given":"Dawid","family":"J\u0119drzkiewicz","sequence":"first","affiliation":[{"name":"Inorganic and Organometallic Chemistry Universit\u00e4t Erlangen-N\u00fcrnberg  Egerlandstrasse 1 91058 Erlangen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jonathan","family":"Mai","sequence":"additional","affiliation":[{"name":"Inorganic and Organometallic Chemistry Universit\u00e4t Erlangen-N\u00fcrnberg  Egerlandstrasse 1 91058 Erlangen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jens","family":"Langer","sequence":"additional","affiliation":[{"name":"Inorganic and Organometallic Chemistry Universit\u00e4t Erlangen-N\u00fcrnberg  Egerlandstrasse 1 91058 Erlangen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zachary","family":"Mathe","sequence":"additional","affiliation":[{"name":"Max Planck Institute for Chemical Energy Conversion  Stiftstr. 34\u201336 45472 M\u00fclheim an der Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Neha","family":"Patel","sequence":"additional","affiliation":[{"name":"Inorganic and Organometallic Chemistry Universit\u00e4t Erlangen-N\u00fcrnberg  Egerlandstrasse 1 91058 Erlangen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Serena","family":"DeBeer","sequence":"additional","affiliation":[{"name":"Max Planck Institute for Chemical Energy Conversion  Stiftstr. 34\u201336 45472 M\u00fclheim an der Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3997-1440","authenticated-orcid":false,"given":"Sjoerd","family":"Harder","sequence":"additional","affiliation":[{"name":"Inorganic and Organometallic Chemistry Universit\u00e4t Erlangen-N\u00fcrnberg  Egerlandstrasse 1 91058 Erlangen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,2,18]]},"reference":[{"key":"e_1_2_3_1_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1150856"},{"key":"e_1_2_3_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp046410h"},{"key":"e_1_2_3_3_1","doi-asserted-by":"publisher","DOI":"10.1071\/CH03006"},{"key":"e_1_2_3_4_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.470476"},{"key":"e_1_2_3_5_1","first-page":"185","volume-title":"Grignard Reagents: New Developments","author":"Garst G. 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