{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,22]],"date-time":"2026-07-22T02:46:38Z","timestamp":1784688398575,"version":"3.55.0"},"reference-count":41,"publisher":"Wiley","issue":"36","license":[{"start":{"date-parts":[[2014,7,23]],"date-time":"2014-07-23T00:00:00Z","timestamp":1406073600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2014,9]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Unsaturated phosphorus compounds, such as phosphaalkenes and phosphaalkynes, show a versatile reactivity in cycloadditions. Although phosphaketenes (R\uf8ffP\uf8feC\uf8feO) have been known for three decades, their chemistry has remained limited. Herein, we show that heteroatom\u2010substituted phosphaketenes, R<jats:sub>3<\/jats:sub>E\uf8ffP\uf8feC\uf8feO (E=Si, Sn), are building blocks for silyl\u2010 and stannyl\u2010substituted five\u2010membered heterocycles containing three phosphorous atoms. The structure of the heterocyclic anion depends on the nature of the tetrel atom involved. Although the silyl analogue [P<jats:sub>3<\/jats:sub>C<jats:sub>2<\/jats:sub>(OSiR<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> is an aromatic 1,2,4\u2010triphospholide, the stannyl compound [P(CO)<jats:sub>2<\/jats:sub>(PSnR<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> is a 1,2,4\u2010triphosphacyclopenta\u20103,5\u2010dionate with a delocalized OCPCO fragment. Because of their anionic character, these compounds can easily be used as building blocks, for example, in the preparation of a silyl\u2010functionalized hexaphosphaferrocene or the parent 1,2,4\u2010triphosphacyclopenta\u20103,5\u2010dionate [P(CO)<jats:sub>2<\/jats:sub>(PH)<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup>. NMR spectroscopic investigations and computations have shown that the heterocycle\u2010formation reactions presented herein are remarkably complex.<\/jats:p>","DOI":"10.1002\/chem.201403419","type":"journal-article","created":{"date-parts":[[2014,7,30]],"date-time":"2014-07-30T06:09:08Z","timestamp":1406700548000},"page":"11326-11330","source":"Crossref","is-referenced-by-count":81,"title":["Phosphaketenes as Building Blocks for the Synthesis of Triphospha Heterocycles"],"prefix":"10.1002","volume":"20","author":[{"given":"Dominikus","family":"Heift","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zolt\u00e1n","family":"Benk\u0151","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hansj\u00f6rg","family":"Gr\u00fctzmacher","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,7,23]]},"reference":[{"key":"e_1_2_3_1_2","unstructured":"\u00a0"},{"key":"e_1_2_3_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3749(199912)625:12<1979::AID-ZAAC1979>3.0.CO;2-S"},{"key":"e_1_2_3_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)87965-4"},{"key":"e_1_2_3_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/om9505470"},{"key":"e_1_2_3_5_2","doi-asserted-by":"crossref","first-page":"1008","DOI":"10.1002\/ange.19830951214","volume":"95","author":"Appel R.","year":"1983","journal-title":"Angew. 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These data can be obtained free of charge from The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk\/data_request\/cif."},{"key":"e_1_2_3_17_2","unstructured":"\u00a0"},{"key":"e_1_2_3_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.19956210109"},{"key":"e_1_2_3_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/0166-1280(94)03946-I"},{"key":"e_1_2_3_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201402884"},{"key":"e_1_2_3_20_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201402884"},{"key":"e_1_2_3_21_2","volume-title":"Organosilicon Chemistry\u2005V","author":"Becker G.","year":"2003"},{"key":"e_1_2_3_22_2","unstructured":"For details on the calculations see the Supporting Information."},{"key":"e_1_2_3_23_2","unstructured":"The second\u2010order perturbation theory analysis of Fock matrix in NBO basis estimates a delocalization energy for each of these interactions of 42.5\u2005kcal\u2009mol\u22121."},{"key":"e_1_2_3_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201308220"},{"key":"e_1_2_3_25_2","unstructured":"We also considered the possibility of the direct formation of [2\u2009c]\u2212from intermediate [A]\u2212and1\u2009cin a [3+2] cycloaddition (thorough the Pb(\u03b4+)\u2010Cb\u2010Pa(\u03b4\u2212)as a dipole and the P\uf8feC bond of1\u2009cas a dipolarophile. However no transition state for this transformation could be found."},{"key":"e_1_2_3_26_2","unstructured":"\u00a0"},{"key":"e_1_2_3_27_2","first-page":"55","volume":"59","author":"Becker G.","year":"1985","journal-title":"Nova Acta Leopold."},{"key":"e_1_2_3_28_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0277-5387(00)83858-9"},{"key":"e_1_2_3_29_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0277-5387(00)80304-6"},{"key":"e_1_2_3_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19991105)5:11<3143::AID-CHEM3143>3.0.CO;2-F"},{"key":"e_1_2_3_31_2","unstructured":"Examples for metal complexes of 1 2 4\u2010triphospholide anions:"},{"key":"e_1_2_3_32_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39870001146"},{"key":"e_1_2_3_33_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(88)80035-4"},{"key":"e_1_2_3_34_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(94)05212-T"},{"key":"e_1_2_3_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.crci.2010.03.031"},{"key":"e_1_2_3_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00215a016"},{"key":"e_1_2_3_37_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-540-68343-8_2"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201403419","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201403419","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T08:45:36Z","timestamp":1760258736000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201403419"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2014,7,23]]},"references-count":41,"journal-issue":{"issue":"36","published-print":{"date-parts":[[2014,9]]}},"alternative-id":["10.1002\/chem.201403419"],"URL":"https:\/\/doi.org\/10.1002\/chem.201403419","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2014,7,23]]}}}