{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,8]],"date-time":"2026-01-08T08:22:25Z","timestamp":1767860545399,"version":"3.49.0"},"reference-count":80,"publisher":"Wiley","issue":"20","license":[{"start":{"date-parts":[[2017,2,6]],"date-time":"2017-02-06T00:00:00Z","timestamp":1486339200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001602","name":"Science Foundation Ireland","doi-asserted-by":"publisher","award":["09\/IN.1\/B2627"],"award-info":[{"award-number":["09\/IN.1\/B2627"]}],"id":[{"id":"10.13039\/501100001602","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2017,4,6]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:italic>P<\/jats:italic>\u2010Alkoxyphosphonium (AP) chlorides were generated by reacting <jats:italic>P<\/jats:italic>\u2010chlorophosphonium chlorides with alcohols. Their well\u2010known spontaneous Arbuzov\u2010type collapse leading to phosphine oxides was studied and its rate found to be dependent on a number of factors in an unexpected fashion: it is inversely proportional to the initial concentration and it shows strong dependence on the acidity of the media but is not very sensitive to the presence of base. To explain these observations, we evoke a self\u2010inhibition model with the formation of the less nucleophilic hydrodichloride anion HCl<jats:sub>2<\/jats:sub> in solution. Detailed analysis of the kinetic data yields the association constant (<jats:italic>K<\/jats:italic>=3\u00d710<jats:sup>2<\/jats:sup>\u2009<jats:sc>m<\/jats:sc><jats:sup>\u22121<\/jats:sup>) of the putative HCl<jats:sub>2<\/jats:sub> species in chloroform. Experimental observations for the collapse of highly enriched diastereomeric alkoxyphosphonium (DAP) chlorides are fully analogous to the achiral AP also implying the involvement of HCl<jats:sub>2<\/jats:sub> anions. Moreover, crystallisation of a highly enriched DAP salt derived from (\u2212)\u2010menthol furnished, for the first time, crystals of individual (<jats:italic>R<\/jats:italic><jats:sub>P<\/jats:sub>)\u2010DAP hydrodichloride as confirmed by X\u2010ray diffractometry. Importantly, the <jats:italic>P<\/jats:italic>\u2010configuration and detailed conformation of the DAP moiety is in good agreement with DFT\u2010level computational results. The thermal collapse of (<jats:italic>R<\/jats:italic><jats:sub>P<\/jats:sub>)\u2010DAP\u22c5HCl<jats:sub>2<\/jats:sub> proceeds with complete retention of the <jats:italic>P<\/jats:italic>\u2010configuration furnishing the phosphine oxide of exceptional enantiomeric purity.<\/jats:p>","DOI":"10.1002\/chem.201604898","type":"journal-article","created":{"date-parts":[[2017,2,6]],"date-time":"2017-02-06T04:33:25Z","timestamp":1486355605000},"page":"4794-4802","source":"Crossref","is-referenced-by-count":10,"title":["Mysterious Decomposition of Alkoxyphosphonium Chlorides: Postulated Involvement of the HCl<sub>2<\/sub> Anion and Its Capture in the Solid State"],"prefix":"10.1002","volume":"23","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1444-234X","authenticated-orcid":false,"given":"Kirill","family":"Nikitin","sequence":"first","affiliation":[{"name":"School of Chemistry, Centre for Synthesis and Chemical Biology University College Dublin  Ireland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Helge","family":"M\u00fcller\u2010Bunz","sequence":"additional","affiliation":[{"name":"School of Chemistry, Centre for Synthesis and Chemical Biology University College Dublin  Ireland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2187-9478","authenticated-orcid":false,"given":"Jimmy","family":"Muldoon","sequence":"additional","affiliation":[{"name":"School of Chemistry, Centre for Synthesis and Chemical Biology University College Dublin  Ireland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1272-4423","authenticated-orcid":false,"given":"Declan G.","family":"Gilheany","sequence":"additional","affiliation":[{"name":"School of Chemistry, Centre for Synthesis and Chemical Biology University College Dublin  Ireland"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2017,2,6]]},"reference":[{"key":"e_1_2_5_1_1","unstructured":"\u00a0"},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.197508011"},{"key":"e_1_2_5_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19750872403"},{"key":"e_1_2_5_3_2","first-page":"387","volume-title":"Organophosphorus Reagents in Organic Synthesis","author":"Appel R.","year":"1979"},{"key":"e_1_2_5_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00165a008"},{"key":"e_1_2_5_5_2","first-page":"53","volume-title":"Organic Mechanisms-Reactions, Stereochemistry and Synthesis","author":"Bruckner R.","year":"2010"},{"key":"e_1_2_5_6_1","unstructured":"\u00a0"},{"key":"e_1_2_5_7_2","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.40.2380"},{"key":"e_1_2_5_8_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1981-29317"},{"key":"e_1_2_5_9_1","unstructured":"\u00a0"},{"key":"e_1_2_5_10_2","first-page":"155","volume-title":"Organophosphorus Reagents in Organic Synthesis","author":"Walker B. J.","year":"1979"},{"key":"e_1_2_5_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00400"},{"key":"e_1_2_5_12_1","unstructured":"\u00a0"},{"key":"e_1_2_5_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/jr9510002550"},{"key":"e_1_2_5_14_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39800000226"},{"key":"e_1_2_5_15_2","volume-title":"Introduction to Organic Chemistry","author":"Streitwieser A.","year":"1981"},{"key":"e_1_2_5_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/P29830001363"},{"key":"e_1_2_5_17_2","doi-asserted-by":"publisher","DOI":"10.1139\/v86-191"},{"key":"e_1_2_5_18_2","first-page":"473","volume":"79","author":"Hudson H. R.","year":"2005","journal-title":"Pol. J. Chem."},{"key":"e_1_2_5_19_1","unstructured":"\u00a0"},{"key":"e_1_2_5_20_2","doi-asserted-by":"publisher","DOI":"10.1039\/P19740000982"},{"key":"e_1_2_5_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/b401301h"},{"key":"e_1_2_5_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/hc.20717"},{"key":"e_1_2_5_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo201085r"},{"key":"e_1_2_5_24_1","unstructured":"\u00a0"},{"key":"e_1_2_5_25_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)71842-9"},{"key":"e_1_2_5_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200390059"},{"key":"e_1_2_5_26_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200390029"},{"key":"e_1_2_5_27_1","unstructured":"\u00a0"},{"key":"e_1_2_5_28_2","doi-asserted-by":"publisher","DOI":"10.1039\/c002825h"},{"key":"e_1_2_5_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol102010h"},{"key":"e_1_2_5_30_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2012.01.067"},{"key":"e_1_2_5_31_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2013.11.098"},{"key":"e_1_2_5_32_1","unstructured":"\u00a0"},{"key":"e_1_2_5_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00518a026"},{"key":"e_1_2_5_34_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1CC14856G"},{"key":"e_1_2_5_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC06389B"},{"key":"e_1_2_5_36_1","unstructured":"\u00a0"},{"key":"e_1_2_5_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja072925l"},{"key":"e_1_2_5_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201000733"},{"key":"e_1_2_5_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201200285"},{"key":"e_1_2_5_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo401318g"},{"key":"e_1_2_5_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja507433g"},{"key":"e_1_2_5_42_1","unstructured":"\u00a0"},{"key":"e_1_2_5_43_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc34136k"},{"key":"e_1_2_5_44_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201309556"},{"key":"e_1_2_5_44_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201309556"},{"key":"e_1_2_5_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b04415"},{"key":"e_1_2_5_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00304a029"},{"key":"e_1_2_5_47_1","doi-asserted-by":"publisher","DOI":"10.1039\/B305375J"},{"key":"e_1_2_5_48_1","unstructured":"The resulting2\u2009a\u22c5Cl is a glassy solid which upon careful drying under vacuum contains about 1\u20132\u2005mol\u2009% residual oxalyl chloride."},{"key":"e_1_2_5_49_1","unstructured":"\u00a0"},{"key":"e_1_2_5_50_2","doi-asserted-by":"publisher","DOI":"10.1039\/jr9600001292"},{"key":"e_1_2_5_51_1","unstructured":"\u00a0"},{"key":"e_1_2_5_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00963a049"},{"key":"e_1_2_5_53_2","doi-asserted-by":"publisher","DOI":"10.1016\/0020-1650(70)80230-6"},{"key":"e_1_2_5_54_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1711944"},{"key":"e_1_2_5_55_1","doi-asserted-by":"publisher","DOI":"10.1039\/cs9800900091"},{"key":"e_1_2_5_56_1","unstructured":"\u00a0"},{"key":"e_1_2_5_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm9706863"},{"key":"e_1_2_5_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic702056y"},{"key":"e_1_2_5_59_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108270113010226"},{"key":"e_1_2_5_60_1","unstructured":"\u00a0"},{"key":"e_1_2_5_61_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar50015a004"},{"key":"e_1_2_5_62_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470171905.ch1"},{"key":"e_1_2_5_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr040087x"},{"key":"e_1_2_5_64_1","unstructured":"\u00a0"},{"key":"e_1_2_5_65_2","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.pc.14.100163.001415"},{"key":"e_1_2_5_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00455a002"},{"key":"e_1_2_5_67_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1387-3806(03)00308-7"},{"key":"e_1_2_5_68_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jasms.2003.11.017"},{"key":"e_1_2_5_69_2","volume-title":"Modern Physical Organic Chemistry","author":"Anslyn E. V.","year":"2006"},{"key":"e_1_2_5_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo801215z"},{"key":"e_1_2_5_71_1","unstructured":"\u00a0"},{"key":"e_1_2_5_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01176a030"},{"key":"e_1_2_5_73_2","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.201300871"},{"key":"e_1_2_5_74_1","unstructured":"\u00a0"},{"key":"e_1_2_5_75_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00832a005"},{"key":"e_1_2_5_76_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1677820"},{"key":"e_1_2_5_77_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00328a025"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201604898","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201604898","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T15:55:45Z","timestamp":1760284545000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201604898"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2017,2,6]]},"references-count":80,"journal-issue":{"issue":"20","published-print":{"date-parts":[[2017,4,6]]}},"alternative-id":["10.1002\/chem.201604898"],"URL":"https:\/\/doi.org\/10.1002\/chem.201604898","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2017,2,6]]}}}