{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,15]],"date-time":"2026-05-15T09:04:15Z","timestamp":1778835855375,"version":"3.51.4"},"reference-count":89,"publisher":"Wiley","issue":"44","license":[{"start":{"date-parts":[[2016,9,15]],"date-time":"2016-09-15T00:00:00Z","timestamp":1473897600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000266","name":"EPSRC","doi-asserted-by":"crossref","id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"crossref"}]},{"name":"SCG Innovation Fund"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2016,10,24]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The ambiphilic nature of geometrically constrained Group\u200515 complexes bearing the <jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2010bis(3,5\u2010di\u2010<jats:italic>tert<\/jats:italic>\u2010butyl\u20102\u2010phenolate)amide pincer ligand (ONO<jats:sup>3\u2212<\/jats:sup>) is explored. Despite their differing reactivity towards nucleophilic substrates with polarised element\u2013hydrogen bonds (e.g., NH<jats:sub>3<\/jats:sub>), both the phosphorus(III), P(ONO) (<jats:bold>1\u2009a<\/jats:bold>), and arsenic(III), As(ONO) (<jats:bold>1\u2009b<\/jats:bold>), compounds exhibit similar reactivity towards charged nucleophiles and electrophiles. Reactions of <jats:bold>1\u2009a<\/jats:bold> and <jats:bold>1\u2009b<\/jats:bold> with KO<jats:italic>t<\/jats:italic>Bu or KNPh<jats:sub>2<\/jats:sub> afford anionic complexes in which the nucleophilic anion associates with the pnictogen centre ([(<jats:italic>t<\/jats:italic>BuO)Pn(ONO)]<jats:sup>\u2212<\/jats:sup> (Pn=P (<jats:bold>2\u2009a<\/jats:bold>), As (<jats:bold>2\u2009b<\/jats:bold>)) and [(Ph<jats:sub>2<\/jats:sub>N)Pn(ONO)]<jats:sup>\u2212<\/jats:sup> (Pn=P (<jats:bold>3\u2009a<\/jats:bold>), As (<jats:bold>3\u2009b<\/jats:bold>)). Compound <jats:bold>2\u2009a<\/jats:bold> can subsequently be reacted with a proton source or benzylbromide to afford the phosphorus(V) compounds (<jats:italic>t<\/jats:italic>BuO)HP(ONO) (<jats:bold>4\u2009a<\/jats:bold>) and (<jats:italic>t<\/jats:italic>BuO)BzP(ONO) (<jats:bold>5\u2009a<\/jats:bold>), respectively, whereas analogous arsenic(V) compounds are inaccessible. Electrophilic substrates, such as HOTf and MeOTf, preferentially associate with the nitrogen atom of the ligand backbone of both <jats:bold>1\u2009a<\/jats:bold> and <jats:bold>1\u2009b<\/jats:bold>, giving rise to cationic species that can be rationalised as either ammonium salts or as amine\u2010stabilised phosphenium or arsenium complexes ([Pn{ON(H)O}]<jats:sup>+<\/jats:sup> (Pn=P (<jats:bold>6\u2009a<\/jats:bold>), As (<jats:bold>6\u2009b<\/jats:bold>)) and [Pn{ON(Me)O}]<jats:sup>+<\/jats:sup> (Pn=P (<jats:bold>7\u2009a<\/jats:bold>), As (<jats:bold>7\u2009b<\/jats:bold>)). Reaction of <jats:bold>1\u2009a<\/jats:bold> with an acid bearing a nucleophilic counteranion (such as HCl) gives rise to a phosphorus(V) compound HPCl(ONO) (<jats:bold>8\u2009a<\/jats:bold>), whereas the analogous reaction with <jats:bold>1\u2009b<\/jats:bold> results in the addition of HCl across one of the As\u2212O bonds to afford ClAs{(H)ONO} (<jats:bold>8\u2009b<\/jats:bold>). Functionalisation at both the pnictogen centre and the ligand backbone is also possible by reaction of <jats:bold>7\u2009a<\/jats:bold>\/<jats:bold>7\u2009b<\/jats:bold> with KO<jats:italic>t<\/jats:italic>Bu, which affords the neutral species (<jats:italic>t<\/jats:italic>BuO)Pn{ON(Me)O} (Pn=P (<jats:bold>9\u2009a<\/jats:bold>), As (<jats:bold>9\u2009b<\/jats:bold>)). The ambiphilic reactivity of these geometrically constrained complexes allows some insight into the mechanism of reactivity of <jats:bold>1\u2009a<\/jats:bold> towards small molecules, such as ammonia and water.<\/jats:p>","DOI":"10.1002\/chem.201603135","type":"journal-article","created":{"date-parts":[[2016,9,15]],"date-time":"2016-09-15T05:05:21Z","timestamp":1473915921000},"page":"15712-15724","source":"Crossref","is-referenced-by-count":39,"title":["On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates"],"prefix":"10.1002","volume":"22","author":[{"given":"Thomas P.","family":"Robinson","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Oxford, Chemistry Research Laboratory  12 Mansfield Road Oxford OX1 3TA UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Siu\u2010Kwan","family":"Lo","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Oxford, Chemistry Research Laboratory  12 Mansfield Road Oxford OX1 3TA UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Daniel","family":"De\u2005Rosa","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Oxford, Chemistry Research Laboratory  12 Mansfield Road Oxford OX1 3TA UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Simon","family":"Aldridge","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Oxford, Chemistry Research Laboratory  12 Mansfield Road Oxford OX1 3TA UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7311-1663","authenticated-orcid":false,"given":"Jose M.","family":"Goicoechea","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Oxford, Chemistry Research Laboratory  12 Mansfield Road Oxford OX1 3TA UK"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2016,9,15]]},"reference":[{"key":"e_1_2_6_1_1","unstructured":"For recent reviews see:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201409800"},{"key":"e_1_2_6_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201409800"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.201100016"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar2001759"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar2000875"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100216y"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200017h"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/C0SC00388C"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature08634"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200903708"},{"key":"e_1_2_6_10_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200903708"},{"key":"e_1_2_6_11_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1141474"},{"key":"e_1_2_6_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200805982"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200805982"},{"key":"e_1_2_6_13_1","unstructured":"\u00a0"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja053247a"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1039\/b813442a"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja805358u"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9068408"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja301042u"},{"key":"e_1_2_6_19_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1134230"},{"key":"e_1_2_6_20_1","unstructured":"\u00a0"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200702908"},{"key":"e_1_2_6_21_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200702908"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201004525"},{"key":"e_1_2_6_22_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201004525"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204007"},{"key":"e_1_2_6_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201204007"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1693"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201307254"},{"key":"e_1_2_6_25_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201307254"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja5006477"},{"key":"e_1_2_6_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/DT9770001328"},{"key":"e_1_2_6_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00331a015"},{"key":"e_1_2_6_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00254a001"},{"key":"e_1_2_6_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00178a022"},{"key":"e_1_2_6_31_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1109389"},{"key":"e_1_2_6_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200503222"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200503222"},{"key":"e_1_2_6_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0731571"},{"key":"e_1_2_6_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja103130u"},{"key":"e_1_2_6_35_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201104745"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201104745"},{"key":"e_1_2_6_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja203538b"},{"key":"e_1_2_6_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja406742n"},{"key":"e_1_2_6_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja407163z"},{"key":"e_1_2_6_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201500453"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201500453"},{"key":"e_1_2_6_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/cen-v071n022.p023"},{"key":"e_1_2_6_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00237a001"},{"key":"e_1_2_6_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja412469e"},{"key":"e_1_2_6_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja302963p"},{"key":"e_1_2_6_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja510558d"},{"key":"e_1_2_6_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja509963m"},{"key":"e_1_2_6_46_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201506998"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201506998"},{"key":"e_1_2_6_47_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201311104"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201311104"},{"key":"e_1_2_6_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.5b01074"},{"key":"e_1_2_6_49_1","doi-asserted-by":"publisher","DOI":"10.1039\/b801115j"},{"key":"e_1_2_6_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200800987"},{"key":"e_1_2_6_51_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201600935"},{"key":"e_1_2_6_52_1","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-0682(199912)1999:12<2295::AID-EJIC2295>3.0.CO;2-F"},{"key":"e_1_2_6_53_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201000901"},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201000901"},{"key":"e_1_2_6_54_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(96)06938-0"},{"key":"e_1_2_6_55_1","unstructured":"A search of the Cambridge Structural Database (version 5.37 November 2015) reveals 114 structurally authenticated species with a three-connect phosphorus atom bonded to three oxygen atoms. The median P\u2212O bond length for these species is 1.627\u2005\u00c5 with a standard deviation of 0.027\u2005\u00c5 a variance of 0.001\u2005\u00c5 and a mean deviation of 0.017\u2005\u00c5."},{"key":"e_1_2_6_56_1","unstructured":"\u00a0"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990419)38:8<1095::AID-ANIE1095>3.0.CO;2-I"},{"key":"e_1_2_6_57_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19990419)111:8<1165::AID-ANGE1165>3.0.CO;2-X"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200800812"},{"key":"e_1_2_6_58_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200800812"},{"key":"e_1_2_6_59_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2SC21458J"},{"key":"e_1_2_6_60_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889886089835"},{"key":"e_1_2_6_61_1","unstructured":"CrysAlisPro Agilent Technologies Version 1.171.35.8."},{"key":"e_1_2_6_62_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889807029238"},{"key":"e_1_2_6_63_1","unstructured":"\u00a0"},{"key":"e_1_2_6_64_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767307043930"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767390000277"},{"key":"e_1_2_6_66_2","unstructured":"SHELX2013 Programs for Crystal Structure Analysis (Release 2013) Sheldrick G.\u2005M. University of G\u00f6ttingen (Germany) 1998."},{"key":"e_1_2_6_67_1","unstructured":"\u00a0"},{"key":"e_1_2_6_68_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.1056"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1007\/s002140050021"},{"key":"e_1_2_6_70_2","unstructured":"ADF2014.01 SCM Theoretical Chemistry Vrije Universiteit: Amsterdam The Netherlands http:\/\/www.scm.com."},{"key":"e_1_2_6_71_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.38.3098"},{"key":"e_1_2_6_72_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.33.8822"},{"key":"e_1_2_6_73_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3382344"},{"key":"e_1_2_6_74_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.454603"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201603135","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201603135","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201603135","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T11:45:43Z","timestamp":1760269543000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201603135"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2016,9,15]]},"references-count":89,"journal-issue":{"issue":"44","published-print":{"date-parts":[[2016,10,24]]}},"alternative-id":["10.1002\/chem.201603135"],"URL":"https:\/\/doi.org\/10.1002\/chem.201603135","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2016,9,15]]}}}