944329-48-0

Upstream product

• 14024-18-1 iron(III)-acetylacetonate 
• 370569-23-6 β-octakis-4-tert-butylphenylcorrolazine 

Downstream Products

• 1428353-80-3 [Fe(octakis(4-tert-butylphenyl)-corrolazinato)(OPPh₃)] 

Relevant academic research and scientific papers

H2O2 oxidations catalyzed by an iron(III) corrolazine: Avoiding high-valent iron-oxido species?

(Chemical Equation Presented) Things aren't always what they seem: The first iron corrolazine complex is shown to activate H2O2 towards sulfide oxidation and peroxide dismutation. Although these reactions are typical of a high-valent iron-oxido species, the data point to a ferric hydroperoxide species as the active oxidant (see scheme).

Formation and characterization of five- and six-coordinate iron(III) corrolazine complexes

Electronic structures of five- and six-coordinate iron(III) corrolazine complexes are determined by means of 1H NMR, 13C NMR, EPR, and M?ssbauer spectroscopy as well as SQUID magnetometry. A series of five-coordinate complexes, [FeIII(TBP8Cz)(L)]* where the axial ligands(L) are cyanide(CN-), imidazole(HIm), 1-methylimidazole(1-MeIm), 4-(N,N-dimethylamino)pyridine(DMAP), pyridine(Py), 4-cyanopyridine(4-CNPy), and tert-butylisocyanide(tBuNC), are obtained by the addition of 1 to 2 equiv. of the ligands to the dichloromethane solutions of FeIII(TBP8Cz) at 298 K: TBP8Cz is a trianion of 2,3,7,8,12,13,17,18-octakis(4-tert-butylphenyl)corrolazine. These complexes commonly show the S = 3/2 at 298 K. By contrast, formation of the six-coordinate complexes depends on the nature of the axial ligands. While the addition of 3 equiv. of CN- has completely converted Fe III(TBP8Cz) to (Bu4N)2[Fe III(TBP8Cz)(CN)2] at 298 K, the conversion to the bis-adduct is only attained below ca. 200 K in the case of HIm, 1-MeIm, and DMAP even in the presence of 50 equiv. of the ligands. If the axial ligand is Py, 4-CNPy, or tBuNC, the formation of [FeIII(TBP 8Cz)(L)2] is confirmed only at an extremely low temperature (15 K). Close inspection of the 1H NMR and EPR spectra has revealed that all the bis-adducts adopt the (dxy) 2(dxz, dyz)3 ground state. While FeIII(TBP8Cz) forms paramagnetic bis- and mono-adduct in toluene solution at 298 K in the presence of excess amount of CN- and tBuNC, respectively, the corresponding porphyrazine complex, [FeIII(TBP8Pz)]Cl, forms diamagnetic bis-CN and bis- tBuNC under the same conditions: TBP8Pz is a dianion of 2,3,7,8,12,13,17,18-octakis(4-tert-butylphenyl)-porphyrazine. Thus, the iron(III) ion of porphyrazine complex is more easily reduced than that of the corresponding corrolazine complex.

A high-valent iron-oxo corrolazine activates C-H bonds via hydrogen-atom transfer

Oxidation of the FeIII complex (TBP8Cz)Fe III [TBP8Cz = octakis(4-tert-butylphenyl)corrolazinate] with O-atom transfer oxidants under a variety of conditions gives the reactive high-valent Fe(O) complex (TBP8Cz+?)Fe IV(O) (2). The solution state structure of 2 was characterized by XAS [d(Fe-O) = 1.64 A]. This complex is competent to oxidize a range of C-H substrates. Product analyses and kinetic data show that these reactions occur via rate-determining hydrogen-atom transfer (HAT), with a linear correlation for log k versus BDE(C-H), and the following activation parameters for xanthene (Xn) substrate: ΔH? = 12.7 ± 0.8 kcal mol -1, ΔS? = -9 ± 3 cal K-1 mol-1, and KIE = 5.7. Rebound hydroxylation versus radical dimerization for Xn is favored by lowering the reaction temperature. These findings provide insights into the factors that control the intrinsic reactivity of Compound I heme analogues.

Catalytic reactivity of a meso-N-substituted corrole and evidence for a high-valent iron-oxo species

It is shown that an iron(III) meso-N-substituted corrole (TBP 8Cz)FeIII (1) (TBP8Cz = octakis(4-tert- butylphenyl)corrolazinato), is a potent catalyst for the oxidation of alkenes in the presence of pentaflouroiodosylbenzene (C6F5IO)as oxidant. In the case of cyclohexene, complex 1 performs on a par wit h one of the best porphyrin catalysts ((TPPF20)FeCl), exhibiting rapid turnover and a high selectivity for epoxide (CzFeIII/C6F 5IO/cyclohexene (1:100:1000) in CH2Cl2/CH 3OH (3:1 v:v) gives 33 turnovers of epoxide in max = 440, 611, 747 nm) under single-turnover-like conditions at -78°C leads to the formation of a new dark-brown species (2) (λmax = 396, 732, 843 nm). The FeIII complex 1 is restored upon the addition of 2 equiv of ferrocene to 2, or by the addition of 1 equiv of PPh3, which concomitantly yields OPPh3. In addition, complex 2 reacts with excess cyclohexene at -42°C to give 1. Complex 2 was also characterized by EPR spectroscopy, and all of the data are consistent with 2 being an antiferromagnetically coupled iron(IV)-oxo ?-cation-radical complex. Rapid-mixing stopped-flow UV-vis studies show that the low-temperature complex 2 is generated as a short-lived intermediate at room temperature.