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Depending on the steric demand of the N\u2010alkyl substituent R, the reaction of disilenide Ar<jats:sub>2<\/jats:sub>Si\uf8feSi(Ar)Li (Ar=2,4,6\u2010<jats:italic>i<\/jats:italic>Pr<jats:sub>3<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>2<\/jats:sub>) with ClP(NR<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub> either affords the phosphinodisilene Ar<jats:sub>2<\/jats:sub>Si\uf8feSi(Ar)P(NR<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub> (for R=<jats:italic>i<\/jats:italic>Pr) or P\u2010amino functionalized phosphasilenes Ar<jats:sub>2<\/jats:sub>(R<jats:sub>2<\/jats:sub>N)Si\uf8ffSi(Ar)\uf8feP(NR<jats:sub>2<\/jats:sub>) (for R=Et, Me) by 1,3\u2010migration of one of the amino groups. In case of R=Me, upon addition of one equivalent of <jats:italic>tert<\/jats:italic>\u2010butylisonitrile a second amino group shift occurs to yield the 1\u2010aza\u20103\u2010phosphaallene Ar<jats:sub>2<\/jats:sub>(R<jats:sub>2<\/jats:sub>N)Si\uf8ffSi(NR<jats:sub>2<\/jats:sub>)(Ar)\uf8ffP\uf8feC\uf8feN<jats:italic>t<\/jats:italic>Bu with pronounced ylidic character. All new compounds were fully characterized by multinuclear NMR spectroscopy as well as single\u2010crystal X\u2010ray diffraction and DFT calculations in selected cases.<\/jats:p>","DOI":"10.1002\/anie.201308525","type":"journal-article","created":{"date-parts":[[2014,1,23]],"date-time":"2014-01-23T23:28:13Z","timestamp":1390519693000},"page":"2216-2220","source":"Crossref","is-referenced-by-count":71,"title":["From Disilene (Si\uf8feSi) to Phosphasilene (Si\uf8feP) and Phosphacumulene (P\uf8feC\uf8feN)"],"prefix":"10.1002","volume":"53","author":[{"given":"Philipp","family":"Willmes","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michael 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