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Examples include rigid, polyvalent arenes and bicyclic compounds featuring strong C\u2500C or C\u2500H bonds. Aliphatic rings are rare in this context due to the challenge of stereochemical control over C\u2500H functionalization. Here we investigate inorganic cyclohexane\u2010like P<jats:sub>2<\/jats:sub>N<jats:sub>4<\/jats:sub> rings (aza\u2010diphosphinanes) and develop a model based on negative hyperconjugation and diaxial strain to explain their <jats:italic>cis<\/jats:italic>\/<jats:italic>trans<\/jats:italic> isomerization. Informed by this model, we rationally make 1,4\u2010disubstituted aza\u2010diphosphinanes, and stereoselectively oxidize them to aza\u2010diphosphazenanes, which retain their <jats:italic>cis<\/jats:italic> (77\u00b0) or <jats:italic>trans<\/jats:italic> (180\u00b0) covalent exit vectors. These compounds show high stability but nevertheless react as 1,4\u2010dinucleophiles, supporting their classification as new cyclohexane\u2010like connectors. Appropriate connector choice in polycondensations enables the divergent synthesis of low\u2010molecular weight macrocyclic oligomers (from the <jats:italic>cis<\/jats:italic> variant) or the first example of high molecular weight cyclo\u2010linear polyphosphazenes (from the <jats:italic>trans<\/jats:italic> variant). These results provide fundamental insight into the stereochemistry of inorganic heterocycles and molecular dimensionality, debut connectors that fill a niche left by organic ones, and offer access to new classes of inorganic polymers for future investigation.<\/jats:p>","DOI":"10.1002\/anie.202503568","type":"journal-article","created":{"date-parts":[[2025,3,11]],"date-time":"2025-03-11T19:53:57Z","timestamp":1741722837000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Aza\u2010Diphosphazenanes: Inorganic Cyclohexane\u2010like Connectors with Stereochemically Tunable Exit Vectors for Molecular and Macromolecular Chemistry"],"prefix":"10.1002","volume":"64","author":[{"given":"Michael A.","family":"Land","sequence":"first","affiliation":[{"name":"Chemistry Department Dalhousie University  6274 Coburg Rd Halifax NS B3H 4R2 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Joseph","family":"Bedard","sequence":"additional","affiliation":[{"name":"Chemistry Department Dalhousie University  6274 Coburg Rd Halifax NS B3H 4R2 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tanner","family":"George","sequence":"additional","affiliation":[{"name":"Department of Chemistry Saint Mary's University  923 Robie St. Halifax NS B3H 3C3 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jason D.","family":"Masuda","sequence":"additional","affiliation":[{"name":"Department of Chemistry Saint Mary's University  923 Robie St. Halifax NS B3H 3C3 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"S. 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