185697-00-1Relevant academic research and scientific papers
Oxidative addition of allylammonium BPh4- to nickel(0): Synthesis, crystal structure, fluxional behavior, and catalytic activity of chiral [(η3-allyl)(NH3)(PCy3)Ni]BPh4
Aresta,Dibenedetto,Quaranta,Lanfranchi,Tiripicchio
, p. 4199 - 4207 (2008/10/08)
The process of oxidative addition of allylammonium tetraphenylborate to nickel was investigated experimentally. The synthesis, fluxional characteristics, crystal structure and the related catalytic activity was analyzed. The process of addition was performed using the selective activation of the N-C allyl bond. X-ray analysis revealed the [(η3-C3H5)Ni(PCy3)(NH3)]+(1+) cation was chiral in nature as a result of the orientations of allyl groups.
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.
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 (2008/10/08)
The reaction of ammonium and iminium tetraphenylborate salts ((CH2=CHCH2NH3)BPh4, [(CH2=CHCH2)HN=CMe2]BPh4, and [(PhCH2)HN=CMe2]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)2NiN≡NNi(PCy3)2 under mild conditions (253-293 K) and describe a very selective N-C or N-H bond activation. (CH2=CHCH2NH3)BPh4 or [(CH2=CHCH2)HN=CMe2]BPh4 react with (Cy3P)2Ni(η2-CO2) and (Cy3P)2NiN≡NNi(PCy3)2 to afford the cationic π-allyl-Ni complexes [(η3-C3H5)Ni(PCy3)(NH 3)]BPh4 (1) and [(η3-C3H5)-Ni(PCy3)(η 1(N)-HN=CMe2)]BPh4 (2), respectively. The reaction of [(PhCH2)HN=CMe2]BPh4 with (Cy3P)2NiN≡NNi(PCy3)2 leads to the hydrido-imino complex [trans-(H)Ni(PCy3)2(η1-(N)-PhCH2N=CMe 2)]BPh4 (3) through N-H 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.
