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These are isolated as mixtures of <jats:italic>in,in<\/jats:italic>\/<jats:italic>out,out<\/jats:italic> isomers that equilibrate with degenerate <jats:italic>in,out<\/jats:italic>\/<jats:italic>out,in<\/jats:italic> isomers at 150\u2009\u00b0C via pyramidal inversion at phosphorus. For the entire series, VT <jats:sup>31<\/jats:sup>P NMR data establish or bound <jats:italic>K<\/jats:italic><jats:sub>eq<\/jats:sub>, rates, and activation parameters for a variety of phenomena, many of which involve homeomorphic isomerizations, topological processes by which certain molecules can turn themselves inside out (e.\u2009g., <jats:italic>in,in<\/jats:italic>\u21cc<jats:italic>out,out<\/jats:italic>). This provides the first detailed mapping of such trends in homologous series of aliphatic bicyclic compounds XE((CH<jats:sub>2<\/jats:sub>)<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub>)<jats:sub>3<\/jats:sub>EX with any type of bridgehead. Isomeric diborane adducts <jats:bold>1\u2009a<\/jats:bold>,<jats:bold>d<\/jats:bold>\u2009\u22c5\u20092BH<jats:sub>3<\/jats:sub> are also characterized. Crystal structures of <jats:italic>out,out<\/jats:italic>\u2010<jats:bold>1\u2009a<\/jats:bold> and <jats:italic>in,in<\/jats:italic>\u2010<jats:bold>1\u2009a<\/jats:bold>\u2009\u22c5\u20092BH<jats:sub>3<\/jats:sub> aid isomer assignments and reveal unusual cage conformations.<\/jats:p>","DOI":"10.1002\/chem.202302200","type":"journal-article","created":{"date-parts":[[2023,9,22]],"date-time":"2023-09-22T11:04:21Z","timestamp":1695380661000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Molecules that Turn Themselves Inside\u2010Out: Tuning <i>in<\/i>\/<i>out<\/i> Equilibria and Homeomorphic Isomerization in Macrobicyclic Dibridgehead Diphosphines P((CH<sub>2<\/sub>)<sub><i>n<\/i><\/sub>)<sub>3<\/sub>P Newly Accessible by Earth\u2010Abundant\u2010Metal Templates"],"prefix":"10.1002","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6426-568X","authenticated-orcid":false,"given":"Samuel R.","family":"Zarcone","sequence":"first","affiliation":[{"name":"Department of Chemistry Texas A&amp;M University P.O. Box 30012 College Station  Texas 77842-3012 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Nattamai","family":"Bhuvanesh","sequence":"additional","affiliation":[{"name":"Department of Chemistry Texas A&amp;M University P.O. Box 30012 College Station  Texas 77842-3012 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7012-4872","authenticated-orcid":false,"given":"John A.","family":"Gladysz","sequence":"additional","affiliation":[{"name":"Department of Chemistry Texas A&amp;M University P.O. 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