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We report a new and scalable synthesis of PN adamantanoid compounds by chlorosilane elimination between bis\u2010silylated amines and phosphorus trichloride. We further study the mechanism of the recently\u2010reported four\u2010fold oxidation of such cages with Me<jats:sub>3<\/jats:sub>SiN<jats:sub>3<\/jats:sub> to yield tetravalent tetrahedral connectors for materials chemistry. Reaction monitoring and kinetic modelling revealed the key rate\u2010limiting step, but attempts to accelerate this using Lewis acid additives were unsuccessful. Nevertheless, a new four\u2010fold oxidized PN\u2010adamantanoid cage has been prepared and structurally characterized.<\/jats:p>","DOI":"10.1002\/asia.202300561","type":"journal-article","created":{"date-parts":[[2023,7,27]],"date-time":"2023-07-27T07:49:20Z","timestamp":1690444160000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["An Improved Synthesis of PN\u2010adamantanoid Cages P<sub>4<\/sub>(NR)<sub>6<\/sub> and a Mechanistic Study of their Fourfold Oxidation"],"prefix":"10.1002","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5861-242X","authenticated-orcid":false,"given":"Michael A.","family":"Land","sequence":"first","affiliation":[{"name":"Department of Chemistry Dalhousie University  6274 Coburg Road Halifax NS, B3H 4R2 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jincheng","family":"Ren","sequence":"additional","affiliation":[{"name":"Department of Chemistry Dalhousie University  6274 Coburg Road Halifax NS, B3H 4R2 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4989-8726","authenticated-orcid":false,"given":"Nicholas J.","family":"Roberts","sequence":"additional","affiliation":[{"name":"Department of Chemistry Dalhousie University  6274 Coburg Road Halifax NS, B3H 4R2 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8493-4844","authenticated-orcid":false,"given":"Karlee L.","family":"Bamford","sequence":"additional","affiliation":[{"name":"Department of Chemistry Dalhousie University  6274 Coburg Road Halifax NS, B3H 4R2 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mohsen","family":"Shayan","sequence":"additional","affiliation":[{"name":"Department of Chemistry Dalhousie University  6274 Coburg Road Halifax NS, B3H 4R2 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Anastasiia","family":"Kutulska","sequence":"additional","affiliation":[{"name":"Department of Chemistry Dalhousie University  6274 Coburg Road Halifax NS, B3H 4R2 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7284-9132","authenticated-orcid":false,"given":"Tanner","family":"George","sequence":"additional","affiliation":[{"name":"Department of Chemistry Saint Mary's University  923 Robie Street Halifax NS, B3H 3C3 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6195-9691","authenticated-orcid":false,"given":"Jason D.","family":"Masuda","sequence":"additional","affiliation":[{"name":"Department of Chemistry Saint Mary's University  923 Robie Street Halifax NS, B3H 3C3 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9180-7907","authenticated-orcid":false,"given":"Saurabh S.","family":"Chitnis","sequence":"additional","affiliation":[{"name":"Department of Chemistry Dalhousie University  6274 Coburg Road Halifax NS, B3H 4R2 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,8,4]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1016\/0277-5387(95)00340-1"},{"key":"e_1_2_8_2_1","unstructured":"\u00a0"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200454234"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.8b04508"},{"key":"e_1_2_8_5_1","unstructured":"\u00a0"},{"key":"e_1_2_8_6_2","first-page":"27","volume":"7","author":"Polarz S.","year":"2011","journal-title":"Inorg. 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