{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,28]],"date-time":"2026-10-28T07:57:42Z","timestamp":1793174262681,"version":"4.5.0"},"reference-count":75,"publisher":"Wiley","issue":"40","license":[{"start":{"date-parts":[[2016,9,1]],"date-time":"2016-09-01T00:00:00Z","timestamp":1472688000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"crossref","award":["SCHU 1170\/11-1"],"award-info":[{"award-number":["SCHU 1170\/11-1"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"crossref"}]},{"name":"Gesellschaft Deutscher Chemiker"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2016,9,26]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    The Group\u200515 open\u2010shell singlet biradicaloid [P(\u03bc\u2010NTer)]\n                    <jats:sub>2<\/jats:sub>\n                    (Ter=2,6\u2010bis(2,4,6\u2010trimethylphenyl)phenyl) was utilized in the activation of stable small molecules. Fast reactions with H\n                    <jats:sub>2<\/jats:sub>\n                    , CO\n                    <jats:sub>2<\/jats:sub>\n                    , and NH\n                    <jats:sub>3<\/jats:sub>\n                    were observed. Dihydrogen easily added to [P(\u03bc\u2010NTer)]\n                    <jats:sub>2<\/jats:sub>\n                    \u2009, yielding [HP(\u03bc\u2010NTer)]\n                    <jats:sub>2<\/jats:sub>\n                    under ambient conditions whereas reversible release of molecular hydrogen was observed at slightly elevated temperatures (\n                    <jats:italic>T<\/jats:italic>\n                    &gt;60\u2009\u00b0C). As [P(\u03bc\u2010NTer)]\n                    <jats:sub>2<\/jats:sub>\n                    is a species with phosphorus in the unusual formal oxidation state +II, it is capable of reducing carbon dioxide to afford a zwitterionic compound, [OP(\u03bc\u2010NTer)\n                    <jats:sub>2<\/jats:sub>\n                    P], and carbon monoxide. The reaction of [P(\u03bc\u2010NTer)]\n                    <jats:sub>2<\/jats:sub>\n                    with ammonia led to the formation of an azadiphosphiridine after rearrangements of the central P\n                    <jats:sub>2<\/jats:sub>\n                    N\n                    <jats:sub>2<\/jats:sub>\n                    heterocycle.\n                  <\/jats:p>","DOI":"10.1002\/anie.201606892","type":"journal-article","created":{"date-parts":[[2016,9,1]],"date-time":"2016-09-01T19:50:42Z","timestamp":1472759442000},"page":"12214-12218","source":"Crossref","is-referenced-by-count":62,"title":["Metal\u2010Free Activation of Hydrogen, Carbon Dioxide, and Ammonia by the Open\u2010Shell Singlet Biradicaloid [P(\u03bc\u2010NTer)]\n                    <sub>2<\/sub>"],"prefix":"10.1002","volume":"55","author":[{"given":"Alexander","family":"Hinz","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Oxford Chemistry Research Laboratory  12 Mansfield Road OX1 3TA Oxford UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9060-7065","authenticated-orcid":false,"given":"Axel","family":"Schulz","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie, Universit\u00e4t Rostock  Albert-Einstein-Strasse 3a 18059 Rostock Germany"},{"name":"Leibniz-Institut f\u00fcr Katalyse e.V. an der Universit\u00e4t Rostock  Albert-Einstein-Strasse 29a 18059 Rostock Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexander","family":"Villinger","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie, Universit\u00e4t Rostock  Albert-Einstein-Strasse 3a 18059 Rostock Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2016,9]]},"reference":[{"key":"e_1_2_2_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200903708"},{"key":"e_1_2_2_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200903708"},{"key":"e_1_2_2_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr068357u"},{"key":"e_1_2_2_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/b925794m"},{"key":"e_1_2_2_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)00339-8"},{"key":"e_1_2_2_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/C0SC00388C"},{"key":"e_1_2_2_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar5003494"},{"key":"e_1_2_2_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr020406p"},{"key":"e_1_2_2_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr400547x"},{"key":"e_1_2_2_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr400056a"},{"key":"e_1_2_2_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr100133q"},{"key":"e_1_2_2_11_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature08634"},{"key":"e_1_2_2_12_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1134230"},{"key":"e_1_2_2_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201208746"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201208746"},{"key":"e_1_2_2_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201302179"},{"key":"e_1_2_2_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4SC00395K"},{"key":"e_1_2_2_16_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1141474"},{"key":"e_1_2_2_17_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0sc00451k"},{"key":"e_1_2_2_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201402874"},{"key":"e_1_2_2_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja900880z"},{"key":"e_1_2_2_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic4007058"},{"key":"e_1_2_2_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201411595"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201411595"},{"key":"e_1_2_2_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201005903"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201005903"},{"key":"e_1_2_2_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201303906"},{"key":"e_1_2_2_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201500570"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201500570"},{"key":"e_1_2_2_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja510558d"},{"key":"e_1_2_2_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja302963p"},{"key":"e_1_2_2_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201506998"},{"key":"e_1_2_2_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201506998"},{"key":"e_1_2_2_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200805982"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200805982"},{"key":"e_1_2_2_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200901403"},{"key":"e_1_2_2_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic500457q"},{"key":"e_1_2_2_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja053247a"},{"key":"e_1_2_2_32_1","doi-asserted-by":"publisher","DOI":"10.1039\/b513189h"},{"key":"e_1_2_2_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja906053y"},{"key":"e_1_2_2_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja055374c"},{"key":"e_1_2_2_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja300111q"},{"key":"e_1_2_2_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic101487g"},{"key":"e_1_2_2_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/om4000049"},{"key":"e_1_2_2_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja3116789"},{"key":"e_1_2_2_39_1","unstructured":"In 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For further information on biradical(oid)s see:"},{"key":"e_1_2_2_40_2","unstructured":"Ref.\u2005[9];"},{"key":"e_1_2_2_41_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2006.09.007"},{"key":"e_1_2_2_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201103742"},{"key":"e_1_2_2_42_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201103742"},{"key":"e_1_2_2_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201208360"},{"key":"e_1_2_2_43_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201208360"},{"key":"e_1_2_2_44_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201408639"},{"key":"e_1_2_2_44_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201408639"},{"key":"e_1_2_2_45_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201403964"},{"key":"e_1_2_2_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic501905v"},{"key":"e_1_2_2_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b00959"},{"key":"e_1_2_2_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00367a007"},{"key":"e_1_2_2_49_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.theochem.2005.12.007"},{"key":"e_1_2_2_50_1","doi-asserted-by":"publisher","DOI":"10.1080\/10426507.2015.1128909"},{"key":"e_1_2_2_51_1","unstructured":"Compound4can also be prepared by reaction of1with TEMPO. Details are given in the Supporting Information."},{"key":"e_1_2_2_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01846a007"},{"key":"e_1_2_2_53_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200901472"},{"key":"e_1_2_2_54_1","unstructured":"M.\u2005J. Frisch et\u2005al. Gaussian\u200909 D.01 Gaussian Inc. Wallingford CT 2009."},{"key":"e_1_2_2_55_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic50223a034"},{"key":"e_1_2_2_56_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200801674"},{"key":"e_1_2_2_56_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200801674"},{"key":"e_1_2_2_57_1","unstructured":"A second possible reaction pathway involves the attack of both O\u2005atoms of the CO2molecule at one P atom leading to the formation of a four-membered spirocyclic intermediate (spiro-3Ph; Table\u2005S5 and Figure\u2005S8) which however is not favored as the energy barrier for the first transition state is much higher (3Ph: 22.7 vs. spiro-3Ph: 60.3\u2005kcal\u2009mol\u22121) and spiro-3Ph represents a high-lying isomer (\u0394G\u00b0298=49.8\u2005kcal\u2009mol\u22121)."},{"key":"e_1_2_2_58_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198103851"},{"key":"e_1_2_2_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19810930421"},{"key":"e_1_2_2_59_1","doi-asserted-by":"publisher","DOI":"10.1515\/znb-1981-1216"},{"key":"e_1_2_2_60_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19911240415"},{"key":"e_1_2_2_61_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19931261005"},{"key":"e_1_2_2_62_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)60641-X"},{"key":"e_1_2_2_63_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CC09164G"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201606892","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201606892","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201606892","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,10,6]],"date-time":"2023-10-06T15:46:33Z","timestamp":1696607193000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201606892"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2016,9]]},"references-count":75,"journal-issue":{"issue":"40","published-print":{"date-parts":[[2016,9,26]]}},"alternative-id":["10.1002\/anie.201606892"],"URL":"https:\/\/doi.org\/10.1002\/anie.201606892","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2016,9]]}}}