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Reactions of the cobalt\u2010hydride complex [Co(P<jats:sub>2<\/jats:sub>C<jats:sub>2<\/jats:sub><jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>H] (<jats:bold>G<\/jats:bold>) with <jats:italic>n<\/jats:italic>BuLi, <jats:italic>t<\/jats:italic>BuLi, or PhLi afforded [Li(solv)<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>{Co(\u03b7<jats:sup>3<\/jats:sup>\u2010P<jats:sub>2<\/jats:sub>C<jats:sub>2<\/jats:sub><jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>HR)(\u03b7<jats:sup>4<\/jats:sup>\u2010P<jats:sub>2<\/jats:sub>C<jats:sub>2<\/jats:sub><jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>)}] (<jats:bold>1<\/jats:bold>: R=<jats:italic>n<\/jats:italic>Bu, (solv)<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>=(Et<jats:sub>2<\/jats:sub>O)<jats:sub>2<\/jats:sub>; <jats:bold>2<\/jats:bold>: R=<jats:italic>t<\/jats:italic>Bu, (solv)<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>=(thf)<jats:sub>2<\/jats:sub>; <jats:bold>3<\/jats:bold>: R=Ph, (solv)<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>=(Et<jats:sub>2<\/jats:sub>O)(thf)<jats:sub>2<\/jats:sub>), with an \u03b7<jats:sup>3<\/jats:sup>\u2010coordinated 1,3\u2010diphosphacyclobutene ligand as a result of organyl\u2010anion attack at one of the phosphorus atoms of the bis(1,3\u2010diphosphacyclobutadiene) backbone. In contrast to the reactions with PhLi, the aryl\u2010magnesium compounds <jats:italic>p<\/jats:italic>\u2010tolyl magnesium chloride and <jats:italic>p<\/jats:italic>\u2010fluorophenyl magnesium bromide deprotonate [Co(P<jats:sub>2<\/jats:sub>C<jats:sub>2<\/jats:sub><jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>H] to give the magnesium salt [Mg(MeCN)<jats:sub>6<\/jats:sub>][Co(\u03b7<jats:sup>4<\/jats:sup>\u2010P<jats:sub>2<\/jats:sub>C<jats:sub>2<\/jats:sub><jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sub>2<\/jats:sub> (<jats:bold>4<\/jats:bold>), which contains a bis(1,3\u2010diphosphacyclobutadiene)\u2010cobaltate anion. The [Co(\u03b7<jats:sup>4<\/jats:sup>\u2010P<jats:sub>2<\/jats:sub>C<jats:sub>2<\/jats:sub><jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> anions are well separated from the octahedral [Mg(MeCN)<jats:sub>6<\/jats:sub>]<jats:sup>2+<\/jats:sup> cation in the molecular structure of <jats:bold>4<\/jats:bold>. Compound <jats:bold>1<\/jats:bold> reacts with Me<jats:sub>3<\/jats:sub>SiCl to give neutral [Co(\u03b7<jats:sup>3<\/jats:sup>\u2010P<jats:sub>2<\/jats:sub>C<jats:sub>2<\/jats:sub><jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>H<jats:italic>n<\/jats:italic>Bu)(\u03b7<jats:sup>4<\/jats:sup>\u2010P<jats:sub>2<\/jats:sub>C<jats:sub>2<\/jats:sub><jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>SiMe<jats:sub>3<\/jats:sub>)] (<jats:bold>5<\/jats:bold>, 52\u2009% yield) with an SiMe<jats:sub>3<\/jats:sub> group attached to one of the P atoms of the previously unfunctionalized backbone.<\/jats:p>","DOI":"10.1002\/chem.201900170","type":"journal-article","created":{"date-parts":[[2019,3,6]],"date-time":"2019-03-06T13:18:44Z","timestamp":1551878324000},"page":"6180-6188","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["1,3\u2010Diphosphacyclobutene Cobalt Complexes"],"prefix":"10.1002","volume":"25","author":[{"given":"Christian","family":"R\u00f6dl","sequence":"first","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  93040 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kai","family":"Schwedtmann","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry Chair of Inorganic Molecular Chemistry TU Dresden  01062 Dresden Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jan J.","family":"Weigand","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry Chair of Inorganic Molecular Chemistry TU Dresden  01062 Dresden Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4066-6483","authenticated-orcid":false,"given":"Robert","family":"Wolf","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  93040 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2019,4,8]]},"reference":[{"volume-title":"Phosphorus: The Carbon Copy","year":"1998","author":"Dillon K. 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