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Herein we describe the formation of rare diphosphan\u20101\u2010ide anions from a P\n                    <jats:sub>5<\/jats:sub>\n                    ligand by treatment with cyanide. Cobalt diorganopentaphosphido complexes have been synthesized by a stepwise reaction sequence involving a low\u2010valent diimine cobalt complex, white phosphorus, and diorganochlorophosphanes. The reactions of the complexes with tetraalkylammonium or potassium cyanide afford a cyclotriphosphido cobaltate anion\n                    <jats:bold>5<\/jats:bold>\n                    and 1\u2010cyanodiphosphan\u20101\u2010ide anions [R\n                    <jats:sub>2<\/jats:sub>\n                    PPCN]\n                    <jats:sup>\u2212<\/jats:sup>\n                    (\n                    <jats:bold>6\u2010R<\/jats:bold>\n                    ). The molecular structure of a related product\n                    <jats:bold>7<\/jats:bold>\n                    suggests a novel reaction mechanism, where coordination of the cyanide anion to the cobalt center induces a ligand rearrangement. This is followed by nucleophilic attack of a second cyanide anion at a phosphorus atom and release of the P\n                    <jats:sub>2<\/jats:sub>\n                    fragment.\n                  <\/jats:p>","DOI":"10.1002\/anie.201908744","type":"journal-article","created":{"date-parts":[[2019,10,1]],"date-time":"2019-10-01T08:34:21Z","timestamp":1569918861000},"page":"18931-18936","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":49,"title":["[3+2] Fragmentation of a Pentaphosphido Ligand by Cyanide"],"prefix":"10.1002","volume":"58","author":[{"given":"Christian M.","family":"Hoidn","sequence":"first","affiliation":[{"name":"University of Regensburg Institute of Inorganic Chemistry 93040 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thomas M.","family":"Maier","sequence":"additional","affiliation":[{"name":"University of Regensburg Institute of Inorganic Chemistry 93040 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Karolina","family":"Trabitsch","sequence":"additional","affiliation":[{"name":"University of Regensburg Institute of Inorganic Chemistry 93040 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7323-7816","authenticated-orcid":false,"given":"Jan J.","family":"Weigand","sequence":"additional","affiliation":[{"name":"TU Dresden Faculty of Chemistry and Food Chemistry 01062 Dresden Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4066-6483","authenticated-orcid":false,"given":"Robert","family":"Wolf","sequence":"additional","affiliation":[{"name":"University of Regensburg Institute of Inorganic Chemistry 93040 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2019,11,7]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9003709"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100010e"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900349u"},{"key":"e_1_2_2_5_1","unstructured":"\u00a0"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2sc00931e"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200305091"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC01572G"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201403581"},{"key":"e_1_2_2_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201403581"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201203908"},{"key":"e_1_2_2_10_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201203908"},{"key":"e_1_2_2_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/C39860001799"},{"key":"e_1_2_2_12_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1168260"},{"key":"e_1_2_2_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b07389"},{"key":"e_1_2_2_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8SC04745F"},{"key":"e_1_2_2_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201904720"},{"key":"e_1_2_2_15_2","doi-asserted-by":"crossref","first-page":"11551","DOI":"10.1002\/ange.201904720","volume":"131","year":"2019","journal-title":"Angew. 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