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We report the N\u2550N bond scission of diazodiarylmethanes, Ar\n                    <jats:sub>2<\/jats:sub>\n                    C\u2550N\u2550N (Ar = phenyl, Ar\n                    <jats:sub>2<\/jats:sub>\n                    C = 9,9\u2010fluorendiyl), mediated by a chelating bis\u2010NHSi (NHSi = N\u2010heterocyclic silylene). Three bis\u2010NHSi scaffolds with tunable Si\u00b7\u00b7\u00b7Si distances were examined: While\n                    <jats:bold>\n                      XT(LSi:)\n                      <jats:sub>2<\/jats:sub>\n                    <\/jats:bold>\n                    (XT = 9,9\u2010dimethyl\u20109H\u2010xanthene\u20104,5\u2010diyl, L = PhC(tBuN)\n                    <jats:sub>2<\/jats:sub>\n                    ) and\n                    <jats:bold>\n                      PhN(LSi:)\n                      <jats:sub>2<\/jats:sub>\n                    <\/jats:bold>\n                    lead to end\u2010on addition products with partial N\u2550N bond activation, the carborane\u2010based\n                    <jats:bold>\n                      CB(LSi:)\n                      <jats:sub>2<\/jats:sub>\n                    <\/jats:bold>\n                    (CB = 1,2\u2010C\n                    <jats:sub>2<\/jats:sub>\n                    B\n                    <jats:sub>10<\/jats:sub>\n                    H\n                    <jats:sub>10<\/jats:sub>\n                    ) engenders complete N\u2550N bond cleavage to afford isolable disilicon nitrido imino species containing a Si\u2550N\u2500Si\u2500N\u2550CAr\n                    <jats:sub>2<\/jats:sub>\n                    unit that hydrolyzes to Ar\n                    <jats:sub>2<\/jats:sub>\n                    C\u2550NH, NH\n                    <jats:sub>3<\/jats:sub>\n                    , SiO\n                    <jats:sub>2<\/jats:sub>\n                    , C\n                    <jats:sub>2<\/jats:sub>\n                    B\n                    <jats:sub>10<\/jats:sub>\n                    H\n                    <jats:sub>12<\/jats:sub>\n                    , and LH. According to density functional theory (DFT) calculations, the N\u2550N cleavage stems from a unique cooperative interaction of the two divalent silicon centers.\n                  <\/jats:p>","DOI":"10.1002\/anie.3873649","type":"journal-article","created":{"date-parts":[[2026,3,19]],"date-time":"2026-03-19T16:24:39Z","timestamp":1773937479000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Bis(silylene)\u2010Mediated N\u2550N Bond Scission of Diazo Compounds"],"prefix":"10.1002","volume":"65","author":[{"given":"Yun","family":"Xiong","sequence":"first","affiliation":[{"name":"Department of Chemistry: Metalorganics and Inorganic Materials Technische Universit\u00e4t Berlin  Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shenglai","family":"Yao","sequence":"additional","affiliation":[{"name":"Department of Chemistry: Metalorganics and Inorganic Materials Technische Universit\u00e4t Berlin  Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9873-4103","authenticated-orcid":false,"given":"Matthias","family":"Driess","sequence":"additional","affiliation":[{"name":"Department of Chemistry: Metalorganics and Inorganic Materials Technische Universit\u00e4t Berlin  Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,3,19]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00224K"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar300101k"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acschembio.6b00810"},{"key":"e_1_2_7_5_1","volume-title":"Diazo Compounds: Properties, Synthesis","author":"Regitz M.","year":"1986"},{"key":"e_1_2_7_6_1","doi-asserted-by":"crossref","unstructured":"S.Gambarotta \u201cNitrogen\u2013Nitrogen Multiple Bond Cleavage and Reduction in Diphenyldiazomethane and Azobenzene by a Titanium (III) Complex \u201dJournal of the Chemical Society Chemical Communications(1982):1015\u20131017.","DOI":"10.1039\/C39820001015"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja8075132"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201910428"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201406191"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc32535g"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2014.07.036"},{"key":"e_1_2_7_12_1","doi-asserted-by":"crossref","unstructured":"F.Basuli L. 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