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These were obtained by double deprotonation of the corresponding primary phosphine\u2010borane precursors RPH<jats:sub>2<\/jats:sub>\u22c5BH<jats:sub>3<\/jats:sub>. Their in\u2010depth structural study, based on multinuclear (<jats:sup>1<\/jats:sup>H, <jats:sup>6<\/jats:sup>Li, <jats:sup>7<\/jats:sup>Li, <jats:sup>11<\/jats:sup>B, <jats:sup>13<\/jats:sup>C, <jats:sup>31<\/jats:sup>P) mono\u2010 and bi\u2010dimensional NMR analyses, indicates a strong influence of the phosphorus substituent on the structure of the gem\u2010dianionic phosphorus structure; a monomeric arrangement was obtained when R=phenyl, whereas a cyclic oligomer was observed for R=cyclohexyl. These compounds represent a new type of useful reagent, and their access paves the way for the concept of \u201cRP synthons\u201d (i.e., RP<jats:sup>2\u2212<\/jats:sup> phosphandiides), likely to be the most flexible precursors of a variety of phosphorus targets.<\/jats:p>","DOI":"10.1002\/chem.201800742","type":"journal-article","created":{"date-parts":[[2018,3,15]],"date-time":"2018-03-15T07:03:59Z","timestamp":1521097439000},"page":"6717-6721","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Synthesis and Identification of Aryl and Alkyl Gem\u2010Dilithium Phosphido\u2010Boranes: A Boost to the Chemistry of Phosphandiides"],"prefix":"10.1002","volume":"24","author":[{"given":"Jie","family":"Guang","sequence":"first","affiliation":[{"name":"Normandie Universit\u00e9, UNIROUEN, INSA de Rouen, CNRS Laboratoire COBRA (UMR 6014 &amp; FR 3038)  76000 Rouen France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Romain","family":"Duwald","sequence":"additional","affiliation":[{"name":"Normandie Universit\u00e9, UNIROUEN, INSA de Rouen, CNRS Laboratoire COBRA (UMR 6014 &amp; FR 3038)  76000 Rouen France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jacques","family":"Maddaluno","sequence":"additional","affiliation":[{"name":"Normandie Universit\u00e9, UNIROUEN, INSA de Rouen, CNRS Laboratoire COBRA (UMR 6014 &amp; FR 3038)  76000 Rouen France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hassan","family":"Oulyadi","sequence":"additional","affiliation":[{"name":"Normandie Universit\u00e9, UNIROUEN, INSA de Rouen, CNRS Laboratoire COBRA (UMR 6014 &amp; FR 3038)  76000 Rouen France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sami","family":"Lakhdar","sequence":"additional","affiliation":[{"name":"Normandie Universit\u00e9, ENSICAEN, UNICAEN, CNRS Laboratoire LCMT (UMR 6507 &amp; FR 3038)  14000 Caen France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Annie\u2010Claude","family":"Gaumont","sequence":"additional","affiliation":[{"name":"Normandie Universit\u00e9, ENSICAEN, UNICAEN, CNRS Laboratoire LCMT (UMR 6507 &amp; FR 3038)  14000 Caen France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8152-7370","authenticated-orcid":false,"given":"Anne","family":"Harrison\u2010Marchand","sequence":"additional","affiliation":[{"name":"Normandie Universit\u00e9, UNIROUEN, INSA de Rouen, CNRS Laboratoire COBRA (UMR 6014 &amp; FR 3038)  76000 Rouen France"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2018,4,22]]},"reference":[{"key":"e_1_2_2_1_1","doi-asserted-by":"publisher","DOI":"10.1007\/3418_2014_74"},{"key":"e_1_2_2_2_1","unstructured":"Among recent leading articles see for instance:"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990115)38:1\/2<92::AID-ANIE92>3.0.CO;2-U"},{"key":"e_1_2_2_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19990115)111:1\/2<97::AID-ANGE97>3.0.CO;2-1"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9839421"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990517)38:10<1483::AID-ANIE1483>3.0.CO;2-D"},{"key":"e_1_2_2_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19990517)111:10<1580::AID-ANGE1580>3.0.CO;2-3"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja001445q"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200461392"},{"key":"e_1_2_2_7_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200461392"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200900830"},{"key":"e_1_2_2_8_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200900830"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja807282s"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/om900364j"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201002483"},{"key":"e_1_2_2_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201002483"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201501818"},{"key":"e_1_2_2_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201501818"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja5114535"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199002951"},{"key":"e_1_2_2_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19901020311"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0023736"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/B405680A"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200400163"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200400318"},{"key":"e_1_2_2_19_1","unstructured":"\u00a0"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199609861"},{"key":"e_1_2_2_20_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19961080912"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/CC9960000305"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic9810485"},{"key":"e_1_2_2_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990917)38:18<2733::AID-ANIE2733>3.0.CO;2-S"},{"key":"e_1_2_2_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19990917)111:18<2906::AID-ANGE2906>3.0.CO;2-B"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(20000515)39:10<1838::AID-ANIE1838>3.0.CO;2-A"},{"key":"e_1_2_2_24_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(20000515)112:10<1908::AID-ANGE1908>3.0.CO;2-C"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200460130"},{"key":"e_1_2_2_25_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200460130"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201000656"},{"key":"e_1_2_2_27_1","unstructured":"Recently Russel Higham and Schreiner have developed \u201cstable\u201d primary phosphines RPH2in which the stabilization is governed by stereoelectronic effects associated to R. These achievements have significantly contributed to the renaissance of primary phosphine chemistry but the restriction to a narrow range of derivatives remains a limitation for further developments. See:"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1039\/a901036j"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200070a"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja4115693"},{"key":"e_1_2_2_31_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2015.03.002"},{"key":"e_1_2_2_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.6b01219"},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b04232"},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201700420"},{"key":"e_1_2_2_34_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201700420"},{"key":"e_1_2_2_35_1","unstructured":"See for instance:"},{"key":"e_1_2_2_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja201760c"},{"key":"e_1_2_2_37_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc30723e"},{"key":"e_1_2_2_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol402197d"},{"key":"e_1_2_2_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201301417"},{"key":"e_1_2_2_40_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC09673E"},{"key":"e_1_2_2_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b03868"},{"key":"e_1_2_2_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00169a036"},{"key":"e_1_2_2_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/om5005995"},{"key":"e_1_2_2_44_1","unstructured":"The main goal here is to study the structure\u2014in solution and in situ\u2014of the reactive species which explains why solid-state analyses by X-ray crystallography is not here put forward as a priority. Indeed an NMR-based analytical strategy warrants that the data obtained correspond to the best possible description of the structures in solution the closest and most representative observation which could be made in the reaction media. In contrast if solid-state structures and X-ray crystallographic data in particular are extremely useful and bring fundamental information on structural arrangements this analytical technique is not necessarily representative of the situation in solution. It brings part of the information but ignores the dynamic that takes place inevitably in the solvent. However with the aim to be as complete as possible both phosphanediide-boranes have been isolated as white solid powders with the hope to isolate crystals by varying the solvent ratios and temperatures but we failed in this perspective. We did not pursue in this direction by adding extra-ligands to chelate the lithium cation a classical solution in such situations since we tried to stay as close as possible to standard reaction conditions."},{"key":"e_1_2_2_45_1","unstructured":"7Li results in larger coupling constants than6Li in the same chemical environment due to its larger gyromagnetic ratio (\u03b3 107\u2005rad\u22c5s\u22121\u22c5T\u22121):\u03b3=3.9371 while\u03b3=10.3976. So7Li\u2005NMR is ideal to observe the splitting pattern. However the line-width of6Li spectra is narrower than that of7Li\u2005NMR because of the smaller quadrupole moment of6Li. Therefore 6Li\u2005NMR is selected for the samples containing different lithium atoms to minimize peak overlapping."},{"key":"e_1_2_2_46_1","unstructured":"\u00a0"},{"key":"e_1_2_2_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar800127e"},{"key":"e_1_2_2_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja810154u"},{"key":"e_1_2_2_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja4059102"},{"key":"e_1_2_2_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja406912h"},{"key":"e_1_2_2_51_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5SC00670H"},{"key":"e_1_2_2_52_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201702990"},{"key":"e_1_2_2_53_1","doi-asserted-by":"publisher","DOI":"10.1021\/om00023a070"},{"key":"e_1_2_2_54_1","unstructured":"Recent reviews:"},{"key":"e_1_2_2_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr400187u"},{"key":"e_1_2_2_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr300295w"},{"key":"e_1_2_2_57_1","unstructured":"Running a Li\u2212P correlation spectrum requires using a very specific probe that is a triple nuclei2H\/7Li\/31P probe. This material is not commercially available and must be built on demand."},{"key":"e_1_2_2_58_1","unstructured":"The difference between the signals observed for the7Li and6Li\u2005NMR spectra at same temperature is most probably due to a similar dynamic of exchange observed at different resonance frequencies (192\u2005MHz and 73\u2005MHz for these two isotopes respectively)."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201800742","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201800742","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T12:50:06Z","timestamp":1760273406000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201800742"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,4,22]]},"references-count":70,"journal-issue":{"issue":"26","published-print":{"date-parts":[[2018,5,7]]}},"alternative-id":["10.1002\/chem.201800742"],"URL":"https:\/\/doi.org\/10.1002\/chem.201800742","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"type":"print","value":"0947-6539"},{"type":"electronic","value":"1521-3765"}],"subject":[],"published":{"date-parts":[[2018,4,22]]},"assertion":[{"value":"2018-02-13","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2018-04-22","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}