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Compound <jats:bold>7<\/jats:bold> reacted with B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> to form the nine\u2010membered heterocyclic product <jats:bold>10<\/jats:bold>, featuring a [P]\u2212C\u2261C\u2212B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> substituent. Compound <jats:bold>7<\/jats:bold> was converted to the bis[P(Mes)vinyl] xanthene derivative <jats:bold>9<\/jats:bold>, which gave the zwitterionic P(H)(Mes)\u2212CH=CH\u2212B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> containing product <jats:bold>16<\/jats:bold> upon treatment with B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>. Thermally induced epimerization barriers at phosphorus of ca. 20 to 27\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup> were calculated by DFT for the alkenyl\u2010 and alkynyl\u2010P derived systems <jats:bold>6<\/jats:bold> to <jats:bold>9<\/jats:bold>, <jats:bold>15<\/jats:bold> and <jats:bold>16<\/jats:bold> and experimentally determined for the examples <jats:bold>7<\/jats:bold> and <jats:bold>16<\/jats:bold>.<\/jats:p>","DOI":"10.1002\/chem.202200248","type":"journal-article","created":{"date-parts":[[2022,2,1]],"date-time":"2022-02-01T11:54:13Z","timestamp":1643716453000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Stereochemical Behavior of Pairs of P\u2010stereogenic Phosphanyl Groups at the Dimethylxanthene 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