185697-08-9Relevant articles and documents
Oxidative addition of ammonium and iminium tetraphenylborates to low-valent metal complexes. Evidence of selective N-C and N-H activation. A new, easy route to cationic allyl- And hydridonickel complexes
Aresta, Michele,Quaranta, Eugenio,Dibenedetto, Angela,Giannoccaro, Potenzo,Tommasi, Immacolata,Lanfranchi, Maurizio,Tiripicchio, Antonio
, p. 834 - 841 (2018/11/27)
The reaction of ammonium and iminium tetraphenylborate salts ((CH2dCHCH2NH3)BPh4, [(CH2dCHCH2)HNdCMe2]BPh4, and [(PhCH2)HNdCMe2]BPh4) with transition-metal systems in a low oxidation state has been investigated. We report the oxidative addition to (Cy3P)2Ni(η2-CO2) or (Cy3P)2NiNtNNi(PCy3)2 under mild conditions (253-293 K) and describe a very selective NsC or NsH bond activation. (CH2dCHCH2NH3)BPh4 or [(CH2dCHCH2)HNdCMe2]BPh4 react with (Cy3P)2Ni(η2-CO2) and (Cy3P)2NiNtNNi(PCy3)2 to afford the cationic π-allyl-Ni complexes [(η3-C3H5)Ni(PCy3)(NH3)]BPh4 (1) and [(η3-C3H5)-Ni(PCy3)(η1(N)-HNdCMe2)]BPh4 (2), respectively. The reaction of [(PhCH2)HNdCMe2]BPh4 with (Cy3P)2NiNtNNi(PCy3)2 leads to the hydrido-imino complex [trans-(H)Ni(PCy3)2(η1-(N)-PhCH2NdCMe2)]BPh4 (3) through NsH bond activation. Complexes 1-3 have been fully characterized in solution by NMR (1H,13C,31P) spectroscopy. The hydrido-imino complex 3, characterized in the solid state by a X-ray diffraction study, shows a distorted-square-planar coordination around the nickel atom with a very narrow P-Ni-P angle, 148.6(2)°, involving the two P atoms from the trans PCy3 ligands.
