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Altogether, these trends imply that the CH versus P substitution enhances ionic P\uf8ffP bond polarization in these compounds. Experimental verification of this hypothesis was obtained for the triphospholyl diazaphospholenes (CR)<jats:sub>2<\/jats:sub>(NR\u2032)<jats:sub>2<\/jats:sub>P\uf8ffP<jats:sub>3<\/jats:sub>(C<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub> (<jats:bold>8\u2009a<\/jats:bold>: R=H, R\u2032=<jats:italic>t<\/jats:italic>Bu; <jats:bold>8\u2009b<\/jats:bold>: R=Me, R\u2032=Mesityl [Mes]), which were prepared through metathesis reactions from suitable precursors and identified by solution and solid\u2010state NMR data and a single\u2010crystal X\u2010ray diffraction study of <jats:bold>8\u2009a<\/jats:bold>. Analysis of <jats:italic>J<\/jats:italic><jats:sub>PP<\/jats:sub> coupling patterns suggested that both species are characterized by the absence of a strong covalent P\uf8ffP bond connecting both rings. This interpretation was confirmed by the finding of a unique P\uf8ffP distance of 2.79\u2005\u00c5 for crystalline <jats:bold>8\u2009a<\/jats:bold>, and further supported by computational studies, which led to the conclusion that both species are better described as diazaphospholenium\u2010triphospholide contact ion pairs rather than covalent molecules. Variable\u2010temperature (VT) NMR spectra of <jats:bold>8\u2009b<\/jats:bold> showed a collapse of <jats:italic>J<\/jats:italic><jats:sub>PP<\/jats:sub> couplings between atoms in different rings, which indicates scrambling of the diazaphospholenium and triphospholide units between different molecules in solution, and further substantiates the proposed view on the molecular structure.<\/jats:p>","DOI":"10.1002\/chem.200902931","type":"journal-article","created":{"date-parts":[[2010,1,22]],"date-time":"2010-01-22T13:18:04Z","timestamp":1264166284000},"page":"2857-2865","source":"Crossref","is-referenced-by-count":16,"title":["Towards Spontaneous Heterolysis of the Homonuclear P\uf8ffP Bond in Diphosphines: The Case of Diazaphospholeniumtriphospholides"],"prefix":"10.1002","volume":"16","author":[{"given":"Zolt\u00e1n","family":"Benk\u0151","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sebastian","family":"Burck","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Dietrich","family":"Gudat","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Martin","family":"Hofmann","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Falk","family":"Lissner","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"L\u00e1szl\u00f3","family":"Nyul\u00e1szi","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ulrich","family":"Zenneck","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2010,2,19]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19921040507"},{"key":"e_1_2_6_1_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199205501"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/b316701a"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19860980124"},{"key":"e_1_2_6_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198600791"},{"key":"e_1_2_6_4_2","unstructured":"\u00a0"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/b004889p"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja010615b"},{"key":"e_1_2_6_7_2","unstructured":"\u00a0"},{"key":"e_1_2_6_8_2","volume-title":"International Tables for Crystallography, Vol\u2005C","author":"Wilson A. 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