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The unusual properties of phospholyl\u20101,3,2\u2010diazaphospholes inspired us to study the coupling of <jats:bold>1<jats:sub>Li<\/jats:sub><\/jats:bold> with chlorodiazaphospholene <jats:bold>2<\/jats:bold>, which led to the N\u2010substituted product <jats:bold>3<\/jats:bold>. Reaction of <jats:bold>1<jats:sub>Li<\/jats:sub><\/jats:bold> with chlorodiphenyl\u2010 and chlorodicyclohexylphosphane likewise gave <jats:italic>N<\/jats:italic>\u2010phosphanylbenzazaphospholes <jats:bold>4<\/jats:bold> and <jats:bold>5<\/jats:bold>, whereas with the more bulky di\u2010<jats:italic>tert<\/jats:italic>\u2010butyl\u2010 and di\u20101\u2010adamantylchlorophosphanes, the diphosphanes <jats:bold>6<\/jats:bold> and <jats:bold>7<\/jats:bold> are obtained; in the case of <jats:bold>7<\/jats:bold> they are isolated as a dimeric LiCl(THF) adduct. Structural information was provided by single\u2010crystal X\u2010ray diffraction and solution NMR spectroscopy experiments. 2D exchange spectroscopy confirmed the existence of two rotamers of the aminophosphane <jats:bold>5<\/jats:bold> at room temperature; variable\u2010temperature NMR spectroscopy studies of <jats:bold>6<\/jats:bold> revealed two dynamic processes, low\u2010temperature inversion at ring phosphorus (\u0394<jats:italic>H<\/jats:italic><jats:sup>\u2260<\/jats:sup>=22\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup>, \u0394<jats:italic>S<\/jats:italic><jats:sup>\u2260<\/jats:sup>=2\u2005J\u2009K<jats:sup>\u22121<\/jats:sup>\u2009mol<jats:sup>\u22121<\/jats:sup>) and very low\u2010temperature rotation of the <jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>P group. Quantum chemical studies give evidence that 2\u2010unsubstituted benzazaphospholides prefer N\u2010phosphanylation, even with bulky chlorophosphanes, and that substituents at the 2\u2010position of the heterocycle are crucial for the occurrence of P\u2013N rotamers and for switching to alternative P\u2010substitution, beyond a threshold steric bulk, by both P\u2010 and 2\u2010position substituents.<\/jats:p>","DOI":"10.1002\/chem.200901753","type":"journal-article","created":{"date-parts":[[2009,10,10]],"date-time":"2009-10-10T06:07:11Z","timestamp":1255154831000},"page":"12263-12272","source":"Crossref","is-referenced-by-count":17,"title":["Ambident PCN Heterocycles: N\u2010 and P\u2010Phosphanylation of Lithium 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