1. Synthesis and Rearrangement of P-Nitroxyl-Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study.
- Author
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Heurich, Tobias, Zheng-Wang Qu, Nozžinović, Senada, Schnakenburg, Gregor, Hideto Matsuoka, Grimme, Stefan, Schiemann, Olav, and Streubel, Rainer
- Subjects
PHOSPHINES ,CHEMICAL synthesis ,OXIDES ,NITROXYL ,CHEMICAL reactions - Abstract
Low-temperature generation of P-nitroxyl phosphane 2 (Ph
2 POTEMP), which was obtained by the reaction of Ph2 PH (1) with two equivalents of TEMPO, is presented. Upon warming, phosphane 2 decomposed to give P-nitroxyl phosphane P-oxide 3 (Ph2 P(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 Ph2 P(S)H (6) or Ph2 P(BH3 )H (11) and TEMPO. Phosphane sulfide 7 revealed a rearrangement to phosphane oxide 8 (Ph2 P(O)STEMP) in CDCl3 at ambient temperature, whereas in THF, thermal decomposition of sulfide 7 yielded salt 10 ([TEMP-H2 ][Ph2 P(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. [ABSTRACT FROM AUTHOR]- Published
- 2016
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