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The DMAP\u2010stabilized zwitterionic \u201chalf\u2010parent\u201d phosphasilene <jats:bold>8<\/jats:bold> is capable of transferring the elusive parent phosphinidene moiety (:PH) to an unsaturated organic substrate, in analogy to the \u201cfree\u201d phosphasilene <jats:bold>4<\/jats:bold>. Furthermore, compounds <jats:bold>4<\/jats:bold> and <jats:bold>8<\/jats:bold> show an unusual reactivity of the Si\uf8feP moiety towards small molecules. They are capable of adding dimethylzinc and of activating the S\uf8ffH bonds in H<jats:sub>2<\/jats:sub>S and the N\uf8ffH bonds in ammonia and several organoamines. Interestingly, the DMAP donor ligand of <jats:bold>8<\/jats:bold> has the propensity to act as a leaving group at the phosphasilene during the reaction. Accordingly, treatment of <jats:bold>8<\/jats:bold> with H<jats:sub>2<\/jats:sub>S affords, under liberation of DMAP, the unprecedented thiosilanoic phosphane LSi\uf8feS(PH<jats:sub>2<\/jats:sub>) <jats:bold>16<\/jats:bold> (L=HC(CMe[2,6\u2010<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>N])<jats:sub>2<\/jats:sub>). Compounds <jats:bold>4<\/jats:bold> and <jats:bold>8<\/jats:bold> react with ammonia both affording L\u2032Si(NH<jats:sub>2<\/jats:sub>)PH<jats:sub>2<\/jats:sub> <jats:bold>17<\/jats:bold>, respectively. In addition, the reaction of <jats:bold>8<\/jats:bold> with isoproylamine, <jats:italic>p<\/jats:italic>\u2010toluidine, and pentafluorophenylhydrazine lead to the corresponding phosphanylsilanes L\u2032Si(PH<jats:sub>2<\/jats:sub>)NHR (R=<jats:italic>i<\/jats:italic>Pr <jats:bold>18\u2009a<\/jats:bold>; R=C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>\uf8ffCH<jats:sub>3<\/jats:sub> <jats:bold>18\u2009b<\/jats:bold>, R=NH(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>) <jats:bold>18\u2009c<\/jats:bold>), respectively.<\/jats:p>","DOI":"10.1002\/chem.201303906","type":"journal-article","created":{"date-parts":[[2014,1,16]],"date-time":"2014-01-16T15:43:13Z","timestamp":1389886993000},"page":"1947-1956","source":"Crossref","is-referenced-by-count":77,"title":["A Donor\u2010Stabilized Zwitterionic \u201cHalf\u2010Parent\u201d Phosphasilene and Its Unusual Reactivity towards Small Molecules"],"prefix":"10.1002","volume":"20","author":[{"given":"Kerstin","family":"Hansen","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tibor","family":"Szilv\u00e1si","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Burgert","family":"Blom","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Elisabeth","family":"Irran","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Matthias","family":"Driess","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,1,16]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)81351-4"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00061a034"},{"key":"e_1_2_6_3_2","doi-asserted-by":"crossref","first-page":"333","DOI":"10.1080\/10426509008038973","volume":"49","author":"van Winkel Y. 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