51455-98-2

Upstream product

• 12582-61-5 μ-oxo-bis[α,β,γ,δ-tetraphenylporphinatoiron] 
• 16456-81-8 meso-tetraphenylporphyrin iron(III) chloride 
• 25482-26-2 5,10,15,20-tetraphenyl porphyrinato iron hydroxide 

Downstream Products

• 16591-56-3 5,10,15,20-tetraphenyl porphyrin iron 
• 12596-60-0 azide radical 
• 114635-47-1 nitridoiron(V)tetraphenylporphyrin 
• 105472-67-1 Fe(C₄₄H₂₈N₄)(C₄H₆N₂)2⁽¹⁺⁾*N₃^(1-)=(Fe(C₄₄H₂₈N₄)(C₄H₆N₂)2)N₃ 

Relevant academic research and scientific papers

Reaction of Sterically Hindered Imidazolate Complexes with Iron Porphyrins

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

Replacement of imidazoles by azide at an iron(III) porphyrin center: Part 1 replacement of N-methylimidazole in bis-(N-methylimidazole) tetraphenylporphyrinato iron(III)

Addition of tetra-n-butylammonium azide to acetone solutions of the tetraphenylporphyrinato iron(III) complex [Fe(TPP)(MeIm)2] +N-3 formed in situ from the reaction of N-methylimidazole and [Fe(TPP)N3] afforded equilibrium amounts of [Fe(TPP)(MeIm)2]+ and [Fe(TPP)(MeIm)N3]. Equilibrium experiments made using a range of known concentrations of added tetra-n-butylammonium azide and N-methylimidazole using stopped-flow apparatus gave an estimate of about 50 for the equilibrium constant for the formation of [Fe(TPP)(MeIm)N3] from the addition of azide to [Fe(TPP)(MeIm) 2]+. Kinetic studies indicated that the substitution of azide ion by N-methylimidazole is a dissociative process, and the results were interpreted using a stationary state approach in which [Fe(TPP)(MeIm)] + was the transient intermediate that discriminated in favor of the reaction with azide as opposed to the reaction with N-methylimidazole by about a factor of two. Loss of N-methylimidazole from [Fe(TPP)(MeIm)2] + is at least 50 times faster than that from the product [Fe(TPP)(MeIm)N3]. Using calculated values of free azide concentrations from experimentally determined ion-pair formation constants led to success in rationalizing results obtained under different conditions.

Hydrogen bonding in metalloporphyrins. Mechanistic study of the reactions of (tetraphenylporphinato)iron(III) azide with imidazole and N-methylimidazole

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.