28829-00-7Relevant academic research and scientific papers
The Mechanism of Nickel-Catalyzed Ethylene Hydrocyanation. Reductive Elimination by an Associative Process
McKinney, Ronald J.,Roe, D. Christopher
, p. 5167 - 5173 (2007/10/02)
The complex (c2H4)L(CN)(C2H5)NiII has been identified at -40 deg C by 1H, 31P, and 13C NMR spectroscopy as the primary intermediate in the catalytic hydrocyanation of ethylene.Reaction of this intermediate with L causes reductive elimination of propanenitrile and produces (C2H4)L2Ni which reacts with ethylene and hydrogen cyanide to regenerate the intermediate.Measurements of second-order rate constants at -50 to -10 deg C result in ΔHexct=8.8 +/- 0.9 kcal/mol and ΔSexct=-34 +/- 4 eu (ΔGexct=16.7 +/- 0.1 kcal/mol at -40 deg C).At higher L concentrations, these nickel species are also in equilibrium with (C2H4)L3Ni, L4Ni, and HNi(CN)L3 which remove nickel from the productive catalytic cycle.Equilibrium constants relating these species and corresponding thermodynamic parameters have been determined.The rates of dissociation of L from L4Ni and HNi(CN)L3 have also been determined.The former reaction is very slow with ΔHexct=20.1 +/- 1.6 kcal/mol and ΔSexct=7 +/- 7 eu (ΔGexct=18.5 kcal/mol at -40 deg C) whereas the latter is about 1E3 faster with ΔHexct=18.8 +/- 2.7 kcal/mol and ΔSexct=17 +/- 10 eu (ΔGexct=14.8 kcal/mol at -40 deg C).
Formation of olefin complexes of Nickel(0). 5. Steric and electronic effects of phosphorus ligands
Tolman,Seidel,Gosser
, p. 1391 - 1396 (2008/10/08)
Spectrophotometric measurements by IR and vis/UV on solutions containing olefins, phosphorus ligands, and nickel(0) show that competition for coordination is strongly affected by both olefin structure and the steric and electronic properties of the phosph
