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In toluene, the reaction of<jats:bold>2<\/jats:bold>with lithium disilenide, R<jats:sub>2<\/jats:sub>Si=Si(R)Li (<jats:bold>1<\/jats:bold>), apparently proceeds via an initial nucleophilic substitution step as well (as suggested by DFT calculations), but affords a saturated bicyclo[1.1.0]butane analogue as the final product, which was further characterized as its Fe(CO)<jats:sub>4<\/jats:sub>complex. In contrast, in 1,2\u2010dimethoxyethane the reaction of<jats:bold>1<\/jats:bold>with<jats:bold>2<\/jats:bold>results in an unprecedented metal\u2013amino exchange reaction.<\/jats:p>","DOI":"10.1002\/anie.201605699","type":"journal-article","created":{"date-parts":[[2016,8,11]],"date-time":"2016-08-11T06:58:19Z","timestamp":1470898699000},"page":"10913-10917","source":"Crossref","is-referenced-by-count":34,"title":["Diverse Reactivity of an Electrophilic Phosphasilene towards Anionic Nucleophiles: Substitution or Metal\u2013Amino Exchange"],"prefix":"10.1002","volume":"55","author":[{"given":"Philipp","family":"Willmes","sequence":"first","affiliation":[{"name":"Krupp-Lehrstuhl f\u00fcr Allgemeine und Anorganische Chemie Universit\u00e4t des Saarlandes 66125 Saarbr\u00fccken Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lukas","family":"Junk","sequence":"additional","affiliation":[{"name":"Krupp-Lehrstuhl f\u00fcr Allgemeine und Anorganische Chemie Universit\u00e4t des Saarlandes 66125 Saarbr\u00fccken Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Volker","family":"Huch","sequence":"additional","affiliation":[{"name":"Krupp-Lehrstuhl f\u00fcr Allgemeine und Anorganische Chemie Universit\u00e4t des Saarlandes 66125 Saarbr\u00fccken Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Cem B.","family":"Yildiz","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Faculty of Science and Letters Aksaray University 68100 Aksaray Turkey"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5600-8034","authenticated-orcid":false,"given":"David","family":"Scheschkewitz","sequence":"additional","affiliation":[{"name":"Krupp-Lehrstuhl f\u00fcr Allgemeine und Anorganische Chemie Universit\u00e4t des Saarlandes 66125 Saarbr\u00fccken Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2016,8,11]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.214.4527.1343"},{"key":"e_1_2_2_3_1","unstructured":"Reviews:"},{"key":"e_1_2_2_4_2","volume-title":"The Chemistry of Organic Silicon Compounds, Vol.\u20053","author":"Weidenbruch M.","year":"2001"},{"key":"e_1_2_2_5_2","volume-title":"The Chemistry of Organic Silicon Compounds, Vol.\u20053","author":"Karni M.","year":"2001"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-3055(05)54003-6"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470669266"},{"key":"e_1_2_2_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr100133q"},{"key":"e_1_2_2_9_1","unstructured":"Reviews:"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1007\/430_2013_119"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5CS00720H"},{"key":"e_1_2_2_12_1","unstructured":"Reviews:"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2011.2"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200801968"},{"key":"e_1_2_2_15_1","unstructured":"\u00a0"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0682(200205)2002:5<1066::AID-EJIC1066>3.0.CO;2-6"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.200400177"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja8061002"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0dt00180e"},{"key":"e_1_2_2_20_1","unstructured":"Reviews:"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1016\/0010-8545(95)09102-5"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2010.312"},{"key":"e_1_2_2_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/om2003442"},{"key":"e_1_2_2_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC04247J"},{"key":"e_1_2_2_25_1","unstructured":"\u00a0"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(96)06483-2"},{"key":"e_1_2_2_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200504145"},{"key":"e_1_2_2_27_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200504145"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1039\/b710888e"},{"key":"e_1_2_2_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201308525"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201308525"},{"key":"e_1_2_2_30_1","unstructured":"\u00a0"},{"key":"e_1_2_2_31_2","doi-asserted-by":"publisher","DOI":"10.1039\/P19940000257"},{"key":"e_1_2_2_32_2","doi-asserted-by":"publisher","DOI":"10.1039\/b412768d"},{"key":"e_1_2_2_33_1","unstructured":"Details on experiments DFT calculations and X-ray diffraction studies ofE-3 5 and5\u22c5Fe(CO)4are supplied in the Supporting Information. 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