51455-98-2Relevant articles and documents
Reaction of Sterically Hindered Imidazolate Complexes with Iron Porphyrins
Brewer, Cynthia T.,Brewer, Greg
, p. 1669 - 1672 (1992)
Reaction of sterically hindered copper(II) or Ni(II) imidazolate complexes derived from imidazole-2-carbaldehyde with iron porphyrins results in the formation of monoadducts which are dinuclear complexes.The spin states of the iron atoms in some of the ad
Hydrogen bonding in metalloporphyrins. Mechanistic study of the reactions of (tetraphenylporphinato)iron(III) azide with imidazole and N-methylimidazole
Byers,Cossham,Edwards,Gordon,Jones,Kenny,Mahmood,McKnight,Sweigart,Tondreau,Wright
, p. 4767 - 4774 (2008/10/08)
The reaction of Fe(TPP)N3 with imidazole (HIm) and N-methylimidazole (MeIm) has been studied in acetone and dichloromethane. Kinetic measurements at room temperature as well as low-temperature spectroscopic, conductivity, and electrochemical studies were used to fully characterize the intermediate complex Fe(TPP)(RIm)N3 as six-coordinate and low spin. This complex reacts further to give Fe(TPP)(RIm)2+N3-. The rate-limiting step in the overall reaction is azide ionization from Fe(TPP)(RIm)N3 to give the high-spin Fe(TPP)(RIm)+N3-. The activation free energy of this step is ca. 3 kcal lower with HIm compared to that with MeIm because of hydrogen bonding to the departing azide ion in the transition state; this acceleration via hydrogen bonding is an entropic effect. A detailed comparison of M(Por-)X systems is presented for M = Fe and Co, Por = TPP, PPIX, and PPIXDME, and X = F-, Cl-, Br-, and N3-. The importance of spin changes on the kinetics and thermodynamics of intermediate and product formation is quantified. Hydrogen-bonding effects are found to have a greater influence on the kinetics than on the thermodynamics. The spin change for the reaction Fe(TPP)(RIm)N3 → Fe(TPP)(RIm)+N3- is S = 1/2 → 5/2, and this is manifested in loss of CFSE (large ΔH?) and a ΔS? about 15 cal deg-1 mol-1 more positive than those found for analogous metalloporphyrin reactions that do not feature a spin change.