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The presence of two differently hybridized phosphorus centers (\u03c3<jats:sup>2<\/jats:sup>,\u03bb<jats:sup>3<\/jats:sup> and \u03c3<jats:sup>3<\/jats:sup>,\u03bb<jats:sup>3<\/jats:sup>) in <jats:bold>5<\/jats:bold> offers the possibility to selectively tune the HOMO\u2013LUMO gap of the compounds by utilizing the different reactivity of the two phosphorus heteroatoms. Oxidation of <jats:bold>5\u2009a<\/jats:bold>\u2013<jats:bold>c<\/jats:bold> by sulfur proceeds exclusively at the \u03c3<jats:sup>3<\/jats:sup>,\u03bb<jats:sup>3<\/jats:sup>\u2010phosphorus atom, thus giving rise to the corresponding thioxophospholes <jats:bold>6\u2009a<\/jats:bold>\u2013<jats:bold>c<\/jats:bold>. Similarly, <jats:bold>5\u2009a<\/jats:bold> is selectively coordinated by AuCl at the \u03c3<jats:sup>3<\/jats:sup>,\u03bb<jats:sup>3<\/jats:sup>\u2010phosphorus atom. Subsequent second AuCl coordination at the \u03c3<jats:sup>2<\/jats:sup>,\u03bb<jats:sup>3<\/jats:sup>\u2010phosphorus heteroatom results in a dimetallic species that is characterized by a gold\u2013gold interaction that provokes a change in \u03c0 conjugation. Spectroscopic, electrochemical, and theoretical investigations show that the phosphaalkene and the phosphole both have a sizable impact on the electronic properties of the compounds. The presence of the phosphaalkene unit induces a decrease of the HOMO\u2013LUMO gap relative to reference phosphole\u2010containing \u03c0 systems that lack a P\uf8feC substituent.<\/jats:p>","DOI":"10.1002\/chem.201402406","type":"journal-article","created":{"date-parts":[[2014,5,30]],"date-time":"2014-05-30T15:43:17Z","timestamp":1401464597000},"page":"8421-8432","source":"Crossref","is-referenced-by-count":30,"title":["Phosphorus Centers of Different Hybridization in Phosphaalkene\u2010Substituted Phospholes"],"prefix":"10.1002","volume":"20","author":[{"given":"Elisabet","family":"\u00d6berg","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andreas","family":"Orthaber","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christophe","family":"Lescop","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"R\u00e9gis","family":"R\u00e9au","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Muriel","family":"Hissler","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sascha","family":"Ott","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,5,30]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/3527607994"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/3527605487"},{"key":"e_1_2_6_4_2","doi-asserted-by":"crossref","DOI":"10.1142\/5194","volume-title":"Molecular Electronics, Commercial Insights, Chemistry, Devices, Architecture and Programming","author":"Tour J. 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