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Chloride abstraction from respective stannyl pnictinidenes [E=P (<jats:bold>5<\/jats:bold>), As (<jats:bold>6<\/jats:bold>), Sb (<jats:bold>7<\/jats:bold>)], which were made accessible by reduction of ECl<jats:sub>3<\/jats:sub> addition products at an intramolecular phosphine\u2010stabilized stannylene, gave the pnictastannenes in moderate yields. The pnictastannenes coordinate Pd(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub> fragments (<jats:bold>12<\/jats:bold>\u2013<jats:bold>14<\/jats:bold>) and the phosphastannene forms also a nickel coordination compound with the Ni(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>\u2010fragment (<jats:bold>11<\/jats:bold>). 2,3\u2010Dimethylbutadiene shows a [2+4]\u2010cycloaddition (<jats:bold>15<\/jats:bold>\u2013<jats:bold>17<\/jats:bold>) in reaction with the pnictastannenes (<jats:bold>8<\/jats:bold>\u2013<jats:bold>10<\/jats:bold>). Products of a [2+2]\u2010addition (<jats:bold>18<\/jats:bold>, <jats:bold>19<\/jats:bold>) were isolated as the phosphaalkyne reaction products for <jats:bold>8<\/jats:bold> and <jats:bold>9<\/jats:bold>. Addition of an O\u2212H bond at the Sn=P\u2010bond was found in reaction of water with phosphastannene <jats:bold>8<\/jats:bold>. Reaction with ammonia afforded the NH<jats:sub>3<\/jats:sub>\u2010adducts (<jats:bold>21<\/jats:bold>\u2013<jats:bold>23<\/jats:bold>) at the tin atom for pnictastannenes <jats:bold>8<\/jats:bold>\u2013<jats:bold>10<\/jats:bold>. Only in the case of the arsastannene an azide reaction product featuring a three membered Sn\u2212As\u2212N\u2010ring was obtained.<\/jats:p>","DOI":"10.1002\/anie.202304200","type":"journal-article","created":{"date-parts":[[2023,4,26]],"date-time":"2023-04-26T06:32:24Z","timestamp":1682490744000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Stiba\u2010, Arsa\u2010 and Phosphastannenes: Syntheses and Reactivities"],"prefix":"10.1002","volume":"62","author":[{"given":"Magda","family":"Zweigart","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Eberhard Karls Universit\u00e4t T\u00fcbingen  Auf der Morgenstelle 18 72076 T\u00fcbingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Clemens","family":"Wenzel","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Eberhard Karls Universit\u00e4t T\u00fcbingen  Auf der 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