81010-33-5Relevant academic research and scientific papers
Kinetics of Monomerization or Polymerization Reaction for Bis(N-phenyl-salicylideneaminato)nickel(II) and Bis(N-methylsalicylideneaminato)nickel(II) in Solid Phase
Miyokawa, Kikuo,Hirashima, Hidenori,Masuda, Isao
, p. 3361 - 3365 (1981)
A kinetic investigation was carried out by means of a thermomagnetic analysis on two structural transformation reactions in solid phase: monomeric square planar-to-polymeric octahedral for Ni(N-Me-salam)2 and polymeric octahedral-to-monomeric square planar for Ni(N-Ph-salam)2.The polymerization process followed the Avrami-Erofeev equation (n=2) with Ea=303 kJ/mol and the monomerization followed the first order equation with Ea=78 kJ/mol.The thermal pyridine liberating reaction of Ni(N-Ph-salam)2py2, involving an octahedral-to-square planar transformation, has beeninvestigated isothermally found to follow the first order equation with Ea=167 kJ/mol.
Steric and conformational effects on the kinetics of ligand substitution in bis(salicylaldiminato)nickel(II) complexes
Schumann, Manfred,Von Holtum, Angela,Wannowius, Klaus J.,Elias, Horst
, p. 606 - 612 (2008/10/08)
Stopped-flow spectrophotometry has been used to study the kinetics of ligand substitution in bis(N-R-salicylaldiminato)nickel(II) complexes I (R = Et, i-Pr, t-Bu) by bidentate ligands HB (acetylacetone, benzoylacetone, dibenzoylmethane, trifluoroacetylacetone, 8-hydroxyquinoline, N-ethylsalicylaldimine) in methanol, 2-propanol, and toluene. A two-term rate law, rate = (kS + kHB[HB])[complex], has been found. The substitution of the first ligand in I is rate determining. Rate constant kS, describing the solvent path, and the corresponding activation parameters ΔH≠ and ΔS≠ do not depend on the nature of the entering ligand for I with R = t-Bu studied in methanol. Rate constant kHB is strongly dependent on the nature of the entering ligand HB. The relative contributions of the two pathways to the overall rate are governed by the conformational equilibrium planar ? tetrahedral of complexes I: the planar isomer favors the ligand-dependent path kHB and the tetrahedral one the solvent path kS. For both pathways mechanisms are derived, which have in common the rate-determining rupture of the Ni-O bond. They differ in that the solvent path is initiated by the attack of an alcohol molecule at the donor oxygen of a coordinated ligand through hydrogen bonding, whereas ligand attack occurs at the metal. The factors influencing the ligand path are the donor ability, acid strength, and stereochemical properties of the entering ligand as well as the Lewis acidity of the substrate. The discussion focuses on a comparison of the nickel system studied with corresponding copper(II) systems and with ligand substitution in square-planar d8 complexes. Additional kinetic information is presented from studies carried out in the solvent mixtures toluene/methanol and toluene/pyridine. The equilibrium constant for the addition of pyridine to complexes I (R = Et, n-Pr, i-Pr, allyl, n-Bu, i-Bu, t-Bu, phenyl) has been determined spectrophotometrically in toluene at 298 K. The individual equilibrium constants for the formation of the mono- (K1) and bis(pyridine) (K2) adduct were calculated (K1 ? K2). The effect of the conformational equilibrium and of self-association on K1 and K2 is discussed.
