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Depending on the electrophile used, the regioselectivity of the functionalization can be adjusted. Using group 16 electrophiles, the trisubstituted compounds [{Cp*Mo}<jats:sub>2<\/jats:sub>{(\u03bc,\u03b7<jats:sup>3\u2009:\u20093<\/jats:sup>\u2010P<jats:sub>3<\/jats:sub>)(\u03bc,\u03b7<jats:sup>1\u2009:\u20091\u2009:\u20091\u2009:\u20091<\/jats:sup>\u20101,3\u2010(SePh)<jats:sub>2<\/jats:sub>\u20102\u2010Br\u2010P<jats:sub>3<\/jats:sub>)}][TEF] (<jats:bold>1<\/jats:bold>), [{Cp*Mo}<jats:sub>2<\/jats:sub>(\u03bc,\u03b7<jats:sup>3\u2009:\u20093<\/jats:sup>\u2010P<jats:sub>3<\/jats:sub>)(\u03bc,\u03b7<jats:sup>1\u2009:\u20091\u2009:\u20091\u2009:\u20091<\/jats:sup>\u20101,2,3\u2010(EPh)<jats:sub>3<\/jats:sub>\u2010P<jats:sub>3<\/jats:sub>)][SbF<jats:sub>6<\/jats:sub>] (E=S (<jats:bold>2<\/jats:bold>), Se (<jats:bold>3<\/jats:bold>)) as well as the side product [{Cp*Mo}<jats:sub>2<\/jats:sub>(\u03bc,\u03b7<jats:sup>4:4<\/jats:sup>\u2010P<jats:sub>4<\/jats:sub>)(\u03bc,\u03b7<jats:sup>1\u2009:\u20091<\/jats:sup>\u2010P(SPh)<jats:sub>2<\/jats:sub>)][SbF<jats:sub>6<\/jats:sub>] (<jats:bold>4<\/jats:bold>) are obtained. By switching to phosphenium ions as group 15 electrophiles, the ring\u2010inserted products [{Cp*Mo}<jats:sub>2<\/jats:sub>(\u03bc,\u03b7<jats:sup>3\u2009:\u20093\u2009:\u20092\u2009:\u20092<\/jats:sup>\u2010P<jats:sub>7<\/jats:sub>R<jats:sub>2<\/jats:sub>)][TEF] (R=Cy (<jats:bold>5<\/jats:bold>), <jats:sup>i<\/jats:sup>Pr (<jats:bold>6<\/jats:bold>)) are isolated, showing an unprecedented P<jats:sub>7<\/jats:sub>R<jats:sub>2<\/jats:sub> structural motif. Furthermore, the reaction with MeOTf yields the dimeric [{Cp*Mo}<jats:sub>4<\/jats:sub>(1,4\u2010Me<jats:sub>2<\/jats:sub>\u2010\u03bc<jats:sub>4<\/jats:sub>,\u03b7<jats:sup>1\u2009:\u20091\u2009:\u20091\u2009:\u20091\u2009:\u20091\u2009:\u20091<\/jats:sup>\u2010P<jats:sub>6<\/jats:sub>)(\u03bc,\u03b7<jats:sup>3\u2009:\u20093<\/jats:sup>\u2010P<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>][TEF]<jats:sub>2<\/jats:sub> (<jats:bold>7<\/jats:bold>) as the first example of a complex featuring two interconnected cyclo\u2010P<jats:sub>6<\/jats:sub> middle deck ligands. Finally, by combination of the methylation step with Ph<jats:sub>2<\/jats:sub>Se<jats:sub>2<\/jats:sub>, the mixed group 14\/16 complex [{Cp*Mo}<jats:sub>2<\/jats:sub>{(\u03bc,\u03b7<jats:sup>3\u2009:\u20093<\/jats:sup>\u2010P<jats:sub>3<\/jats:sub>)(\u03bc,\u03b7<jats:sup>1\u2009:\u20091\u2009:\u20091\u2009:\u20091<\/jats:sup>1,2\u2010(SePh)<jats:sub>2<\/jats:sub>\u20103\u2010Me\u2010P<jats:sub>3<\/jats:sub>)}][OTf] (<jats:bold>8<\/jats:bold>) is obtained.<\/jats:p>","DOI":"10.1002\/chem.202304183","type":"journal-article","created":{"date-parts":[[2024,1,19]],"date-time":"2024-01-19T10:19:48Z","timestamp":1705659588000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Electrophilic Functionalization of a Hexaphosphabenzene Ligand in [(Cp*Mo)<sub>2<\/sub>(\u03bc,\u03b7<sup>6\u2009:\u20096<\/sup>\u2010P<sub>6<\/sub>)]"],"prefix":"10.1002","volume":"30","author":[{"given":"Maximilian","family":"Widmann","sequence":"first","affiliation":[{"name":"Department of Inorganic Chemistry University of Regensburg  Universit\u00e4tsstra\u00dfe 31 93053 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Christoph","family":"Riesinger","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry University of Regensburg  Universit\u00e4tsstra\u00dfe 31 93053 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Robert","family":"Szlosek","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry University of Regensburg  Universit\u00e4tsstra\u00dfe 31 93053 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3497-7082","authenticated-orcid":false,"given":"G\u00e1bor","family":"Bal\u00e1zs","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry University of Regensburg  Universit\u00e4tsstra\u00dfe 31 93053 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2182-5020","authenticated-orcid":false,"given":"Manfred","family":"Scheer","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry University of Regensburg  Universit\u00e4tsstra\u00dfe 31 93053 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,2,13]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"P.\u2005Y. 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