Synthesis and Rearrangement of P‐Nitroxyl‐Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study |
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| Authors: | Tobias Heurich Dr Zheng‐Wang Qu Dr Senada No?inovi? Dr Gregor Schnakenburg Dr Hideto Matsuoka Prof?Dr Stefan Grimme Prof?Dr Olav Schiemann Prof?Dr Rainer Streubel |
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| Institution: | 1. Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universit?t Bonn, Bonn, Germany;2. Mulliken Center for Theoretical Chemistry, Rheinische Friedrich-Wilhelms-Universit?t Bonn, Bonn, Germany;3. Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universit?t Bonn, Bonn, Germany |
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| Abstract: | Low‐temperature generation of P‐nitroxyl phosphane 2 (Ph2POTEMP), which was obtained by the reaction of Ph2PH ( 1 ) with two equivalents of TEMPO, is presented. Upon warming, phosphane 2 decomposed to give P‐nitroxyl phosphane P‐oxide 3 (Ph2P(O)OTEMP) as one of the final products. This facile synthetic protocol also enabled access to P‐sulfide and P‐borane derivatives 7 and 13 , respectively, by using Ph2P(S)H ( 6 ) or Ph2P(BH3)H ( 11 ) and TEMPO. Phosphane sulfide 7 revealed a rearrangement to phosphane oxide 8 (Ph2P(O)STEMP) in CDCl3 at ambient temperature, whereas in THF, thermal decomposition of sulfide 7 yielded salt 10 (TEMP‐H2]Ph2P(S)O]). As well as EPR and detailed NMR kinetic studies, indepth theoretical studies provided an insight into the reaction pathways and spin‐density distributions of the reactive intermediates. |
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| Keywords: | density functional calculations EPR spectroscopy nitroxyl TEMPO phosphanes |
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