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In contrast to similar reactions reported for \u03b2\u2010diketiminate coordinated counterparts of\n                    <jats:bold>3<\/jats:bold>\n                    , these C\u2212H activations proceed with little regioselectivity, though they are considerably faster. Reaction of\n                    <jats:bold>3<\/jats:bold>\n                    with an excess of the pyridine,\n                    <jats:italic>p<\/jats:italic>\n                    \u2010NC\n                    <jats:sub>5<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    Bu\n                    <jats:sup>\n                      <jats:italic>t<\/jats:italic>\n                    <\/jats:sup>\n                    (py\n                    <jats:sup>\n                      Bu\n                      <jats:italic>t<\/jats:italic>\n                    <\/jats:sup>\n                    ), gave [(Priso)Mg(py\n                    <jats:sup>\n                      Bu\n                      <jats:italic>t<\/jats:italic>\n                    <\/jats:sup>\n                    H)(py\n                    <jats:sup>\n                      Bu\n                      <jats:italic>t<\/jats:italic>\n                    <\/jats:sup>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:bold>10<\/jats:bold>\n                    , presumably via reduction of the pyridine to yield a radical intermediate, [(Priso)Mg(py\n                    <jats:sup>\n                      Bu\n                      <jats:italic>t<\/jats:italic>\n                    <\/jats:sup>\n                    \u22c5)(py\n                    <jats:sup>\n                      Bu\n                      <jats:italic>t<\/jats:italic>\n                    <\/jats:sup>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:bold>11<\/jats:bold>\n                    , which then abstracts a proton from the reaction solvent or a reactant. DFT calculations suggest two possible pathways to the observed arene C\u2212H activations. One of these involves photochemical cleavage of the Mg\u2212Mg bond of\n                    <jats:bold>3<\/jats:bold>\n                    , generating magnesium(I) doublet radicals, (Priso)Mg\u22c5. These then doubly reduce the arene substrate to give \u201cBirch\u2010like\u201d products, which subsequently rearrange via C\u2212H activation of the arene. Circumstantial evidence for the photochemical generation of transient magnesium radical species includes the fact that irradiation of a cyclohexane solution of\n                    <jats:bold>3<\/jats:bold>\n                    leads to an intramolecular aliphatic C\u2212H activation process and formation of an alkyl\u2010bridged magnesium(II) species, [{Mg(\u03bc\u2010Priso\n                    <jats:sup>\u2212H<\/jats:sup>\n                    )}\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:bold>12<\/jats:bold>\n                    . Furthermore, irradiation of a 1\u2009:\u20091 mixture of\n                    <jats:bold>3<\/jats:bold>\n                    and the \u03b2\u2010diketiminato dimagnesium(I) compound, [{(\n                    <jats:sup>Dip<\/jats:sup>\n                    Nacnac)Mg}\n                    <jats:sub>2<\/jats:sub>\n                    ] (\n                    <jats:sup>Dip<\/jats:sup>\n                    Nacnac=[HC(MeCNDip)\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>\u2212<\/jats:sup>\n                    ), effects a \u201cscrambling\u201d reaction, and the near quantitative formation of an unsymmetrical dimagnesium(I) compound, [(Priso)Mg\u2212Mg(\n                    <jats:sup>Dip<\/jats:sup>\n                    Nacnac)]\n                    <jats:bold>13<\/jats:bold>\n                    . Finally, the EPR spectrum (77\u2005K) of a glassed solution of UV irradiated\n                    <jats:bold>3<\/jats:bold>\n                    is dominated by a broad featureless signal, indicating the presence of a doublet radical species.\n                  <\/jats:p>","DOI":"10.1002\/chem.202202103","type":"journal-article","created":{"date-parts":[[2022,8,26]],"date-time":"2022-08-26T05:06:53Z","timestamp":1661490413000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":27,"title":["C\u2212H Activation of Inert Arenes using a Photochemically Activated Guanidinato\u2010Magnesium(I) Compound"],"prefix":"10.1002","volume":"28","author":[{"given":"Jeremy C.","family":"Mullins","sequence":"first","affiliation":[{"name":"School of Chemistry PO Box 23 Monash University  Melbourne, &lt;countryPartVIC 3800 Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"K.","family":"Yuvaraj","sequence":"additional","affiliation":[{"name":"School of Chemistry PO Box 23 Monash University  Melbourne, &lt;countryPartVIC 3800 Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yixiao","family":"Jiang","sequence":"additional","affiliation":[{"name":"School of Chemistry PO Box 23 Monash University  Melbourne, &lt;countryPartVIC 3800 Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"suffix":"III","given":"Gerard P.","family":"Van Trieste","sequence":"additional","affiliation":[{"name":"Department of Chemistry Texas A&amp;M University College Station, TX 77843  USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Asim","family":"Maity","sequence":"additional","affiliation":[{"name":"Department of Chemistry Texas A&amp;M University College Station, TX 77843  USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3717-2001","authenticated-orcid":false,"given":"David C.","family":"Powers","sequence":"additional","affiliation":[{"name":"Department of Chemistry Texas A&amp;M University College Station, TX 77843  USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7269-1045","authenticated-orcid":false,"given":"Cameron","family":"Jones","sequence":"additional","affiliation":[{"name":"School of Chemistry PO Box 23 Monash University  Melbourne, &lt;countryPartVIC 3800 Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,9,26]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"See for example:"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1038\/417507a"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1607"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.molcata.2016.06.020"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900206p"},{"key":"e_1_2_8_6_2","unstructured":"J.\u2005J. 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