The reactivity of ammonium- and iminium-BPh4 salts, [CH2/CHCH2NH3]BPh4, [(CH2/CHCH2)HN/CMe2]BPh4 and [(PhCH2)HN/CMe2]BPh4, towards Pd(0)-complexes, [Pd(dppe)(dba)] and [Pd(dppe)2] (dppe/1,2-bis(diphenylphosphino)ethane; dba/dibenzylideneacetone), has been investigated. Allyl-ammonium and -iminium tetraphenylborates [CH2/CHCH2NH3]BPh4 and [(CH2/CHCH2)HN/CMe2]BPh4 react with [Pd(dppe)(dba)] to afford, under mild conditions (293 K), [(h3- C3H5)Pd(dppe)][BPh4], through selective oxidative transfer of allyl group from the ammonium or iminium cation to the Pd center. [(PhCH2)HN/CMe2]BPh4 reacts with [Pd(dppe)2] to afford [H/Pd(dppe)2][BPh4], that, under the reaction conditions, has poor stability as it undergoes hydride transfer to the iminium ion present in the reaction medium, affording [Pd(dppe)2][BPh4]2.
Reactivity of Ammonium and Iminium Tetraphenylborates towards Pd(0)-Complexes: Selective Allyl or Proton Transfer to Pd(0). Evidence of Formation of the Species [HPd(dppe)2]BPh4
QUARANTA, Eugenio;
2002-01-01
Abstract
The reactivity of ammonium- and iminium-BPh4 salts, [CH2/CHCH2NH3]BPh4, [(CH2/CHCH2)HN/CMe2]BPh4 and [(PhCH2)HN/CMe2]BPh4, towards Pd(0)-complexes, [Pd(dppe)(dba)] and [Pd(dppe)2] (dppe/1,2-bis(diphenylphosphino)ethane; dba/dibenzylideneacetone), has been investigated. Allyl-ammonium and -iminium tetraphenylborates [CH2/CHCH2NH3]BPh4 and [(CH2/CHCH2)HN/CMe2]BPh4 react with [Pd(dppe)(dba)] to afford, under mild conditions (293 K), [(h3- C3H5)Pd(dppe)][BPh4], through selective oxidative transfer of allyl group from the ammonium or iminium cation to the Pd center. [(PhCH2)HN/CMe2]BPh4 reacts with [Pd(dppe)2] to afford [H/Pd(dppe)2][BPh4], that, under the reaction conditions, has poor stability as it undergoes hydride transfer to the iminium ion present in the reaction medium, affording [Pd(dppe)2][BPh4]2.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
