{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T14:08:19Z","timestamp":1789740499430,"version":"4.0.1"},"reference-count":86,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T00:00:00Z","timestamp":1789689600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T00:00:00Z","timestamp":1789689600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["426795949"],"award-info":[{"award-number":["426795949"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000781","name":"European Research Council","doi-asserted-by":"publisher","award":["772299"],"award-info":[{"award-number":["772299"]}],"id":[{"id":"10.13039\/501100000781","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"abstract":"ABSTRACT<\/jats:title>\n \n We report a method for converting white phosphorus (P\n 4<\/jats:sub>\n ) directly into tetra\u2010 and pentaphosphanes using\n N<\/jats:italic>\n \u2010heterocyclic carbene (NHC) copper(I) complexes. The insertion of P\n 4<\/jats:sub>\n into the metal\u2010element bonds of the NHC complexes (6Dipp)Cu(Nu) [Nu\u00a0=\u00a0O\n t<\/jats:italic>\n Bu and N(\n i<\/jats:italic>\n Pr)\n 2<\/jats:sub>\n ] affords [(6Dipp)Cu(\n \u03ba<\/jats:italic>\n 2<\/jats:sup>\n \u2010P\n 4<\/jats:sub>\n O\n t<\/jats:italic>\n Bu)] (\n 1<\/jats:bold>\n ) and [(6Dipp)Cu{\n \u03ba<\/jats:italic>\n 2<\/jats:sup>\n \u2010P\n 4<\/jats:sub>\n N(\n i<\/jats:italic>\n Pr)\n 2<\/jats:sub>\n }] (\n 3<\/jats:bold>\n ), which exhibit rotation of the [P\n 4<\/jats:sub>\n Nu]\n \u2212<\/jats:sup>\n ligand around the copper center in solution. This fluxional process is suppressed at low temperature, as shown by variable\u2010temperature\n 31<\/jats:sup>\n P{\n 1<\/jats:sup>\n H} NMR spectroscopy. Treatment of\n 1<\/jats:bold>\n with W(CO)\n 5<\/jats:sub>\n (thf) resulted in the formation of the bimetallic complex [(6Dipp)Cu(\u03bc,\n \u03ba<\/jats:italic>\n 2<\/jats:sup>\n :\n \u03ba<\/jats:italic>\n 1<\/jats:sup>\n \u2010P\n 4<\/jats:sub>\n O\n t<\/jats:italic>\n Bu){W(CO)\n 5<\/jats:sub>\n }] (\n 2<\/jats:bold>\n ) which does not show fluxional behavior. Reactions of\n 1<\/jats:bold>\n and\n 3<\/jats:bold>\n with p\u2010block element halides release metal\u2010free asymmetrically substituted bicyclo[1.1.0]tetraphosphabutane \u2018butterfly\u2019 compounds. The polyphosphanes P\n 4<\/jats:sub>\n (PMes\n 2<\/jats:sub>\n )(O\n t<\/jats:italic>\n Bu) (\n 4a<\/jats:bold>\n ), P\n 4<\/jats:sub>\n [P{N(\n i<\/jats:italic>\n Pr)\n 2<\/jats:sub>\n }\n 2<\/jats:sub>\n ](O\n t<\/jats:italic>\n Bu) (\n 4b<\/jats:bold>\n ), P\n 4<\/jats:sub>\n [P{N(\n i<\/jats:italic>\n Pr)\n 2<\/jats:sub>\n }\n 2<\/jats:sub>\n ]{N(\n i<\/jats:italic>\n Pr)\n 2<\/jats:sub>\n } (\n 4c<\/jats:bold>\n ), and P\n 4<\/jats:sub>\n (BPh\n 2<\/jats:sub>\n ){N(\n i<\/jats:italic>\n Pr)\n 2<\/jats:sub>\n } (\n 5<\/jats:bold>\n ) were isolated as stable compounds. Treatment of\n 4c<\/jats:bold>\n with the NHC IMes induces further phosphorus\u2013phosphorus bond cleavage and rearrangement to give NHC\u2010phosphinidene adduct [\n cyclo<\/jats:italic>\n \u2010P\n 3<\/jats:sub>\n {N(\n i<\/jats:italic>\n Pr)\n 2<\/jats:sub>\n }(P{N(\n i<\/jats:italic>\n Pr)\n 2<\/jats:sub>\n }\n 2<\/jats:sub>\n )(P\u2550IMes)] (\n 6<\/jats:bold>\n ). Compound\n 4c<\/jats:bold>\n also reacts with W(CO)\n 5<\/jats:sub>\n (thf) and CuBr\u00b7SMe\n 2<\/jats:sub>\n to give coordination complexes [W(CO)\n 5<\/jats:sub>\n {\n \u03ba<\/jats:italic>\n 1<\/jats:sup>\n \u2010P\n 4<\/jats:sub>\n (P{N(\n i<\/jats:italic>\n Pr)\n 2<\/jats:sub>\n }\n 2<\/jats:sub>\n )(N{\n i<\/jats:italic>\n Pr}\n 2<\/jats:sub>\n )}] (\n 7<\/jats:bold>\n ) and [Cu(Br){\n \u03ba<\/jats:italic>\n 2<\/jats:sup>\n \u2010P\n 4<\/jats:sub>\n (P{N(\n i<\/jats:italic>\n Pr)\n 2<\/jats:sub>\n }\n 2<\/jats:sub>\n )(N{\n i<\/jats:italic>\n Pr}\n 2<\/jats:sub>\n )}] (\n 8<\/jats:bold>\n ), respectively, demonstrating the ability of\n 4c<\/jats:bold>\n to serve as a mono\u2010 and bidentate ligand for transition metals. All compounds were characterized crystallographically and spectroscopically.\n <\/jats:p>","DOI":"10.1002\/anie.8252739","type":"journal-article","created":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T13:50:33Z","timestamp":1789739433000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["NHC\u2010Copper(I)\u2010Mediated Functionalization of White Phosphorus"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5027-450X","authenticated-orcid":false,"given":"Thomas M.","family":"Horsley Downie","sequence":"first","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-3106-2836","authenticated-orcid":false,"given":"Sophia A.","family":"Vogler","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3497-7082","authenticated-orcid":false,"given":"G\u00e1bor","family":"Bal\u00e1zs","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Francesco","family":"Cirigliano","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg Regensburg 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":"Institute of Inorganic Chemistry University of Regensburg Regensburg 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reaction was also carried out using the more common 5\u2010membered NHC IPr as a supporting ligand. However [(IPr)Cu(\u03ba2\u2010P4OtBu)] was found to have limited stability in solution and thus was not extensively examined. 6Dipp was selected as a supporting ligand as it has been reported to imbue some (NHC)\u2010copper(I) complexes with greater stability (see References84\u201386). Partial characterisation of [(IPr)Cu(\u03ba2\u2010P4OtBu)] by single\u2010crystal\u00a0XRD and NMR spectroscopy and its decomposition over time can be found in the Supporting Information."},{"key":"e_1_2_8_52_1","doi-asserted-by":"publisher","DOI":"10.1039\/c1dt10572h"},{"key":"e_1_2_8_53_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201201330"},{"key":"e_1_2_8_54_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201305315"},{"key":"e_1_2_8_55_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.7b01138"},{"key":"e_1_2_8_56_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201701380"},{"key":"e_1_2_8_57_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198205442"},{"key":"e_1_2_8_58_1","doi-asserted-by":"publisher","DOI":"10.1039\/C39950001383"},{"key":"e_1_2_8_59_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.202000923"},{"key":"e_1_2_8_60_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5DT02757H"},{"key":"e_1_2_8_61_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198109672"},{"key":"e_1_2_8_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.3c02141"},{"key":"e_1_2_8_63_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CS00697J"},{"key":"e_1_2_8_64_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0277\u20105387(00)83446\u20104"},{"key":"e_1_2_8_65_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7DT04034B"},{"key":"e_1_2_8_66_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202408423"},{"key":"e_1_2_8_67_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202110619"},{"key":"e_1_2_8_68_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.202401895"},{"key":"e_1_2_8_69_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201702067"},{"key":"e_1_2_8_70_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200703055"},{"key":"e_1_2_8_71_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja077296u"},{"key":"e_1_2_8_72_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200902344"},{"key":"e_1_2_8_73_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201301137"},{"key":"e_1_2_8_74_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3DT02690F"},{"key":"e_1_2_8_75_1","doi-asserted-by":"publisher","DOI":"10.1039\/D6SC02577C"},{"key":"e_1_2_8_76_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.6b01163"},{"key":"e_1_2_8_77_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201800459"},{"key":"e_1_2_8_78_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2025.102649"},{"key":"e_1_2_8_79_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201506784"},{"key":"e_1_2_8_80_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201703175"},{"key":"e_1_2_8_81_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202005025"},{"key":"e_1_2_8_82_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201703953"},{"key":"e_1_2_8_83_1","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201908998"},{"key":"e_1_2_8_84_1","unstructured":"Deposition numbers 2491197\u20132491204 2577702\u20132577704 and 2584727 contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service."},{"key":"e_1_2_8_85_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.6b00025"},{"key":"e_1_2_8_86_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1DT03540A"},{"key":"e_1_2_8_87_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.2c02199"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.8252739","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.8252739","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.8252739","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T13:50:36Z","timestamp":1789739436000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.8252739"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,18]]},"references-count":86,"alternative-id":["10.1002\/anie.8252739"],"URL":"https:\/\/doi.org\/10.1002\/anie.8252739","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,18]]},"assertion":[{"value":"2026-07-31","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-09-09","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-09-18","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e8252739"}}