Functional Model of Compound II of Cytochrome P450: Spectroscopic Characterization and Reactivity Studies of a FeIV-OH Complex.

Herein, we show that the reaction of a mononuclear FeIII(OH) complex (1) with N-tosyliminobenzyliodinane (PhINTs) resulted in the formation of a FeIV(OH) species (3). The obtained complex 3 was characterized by an array of spectroscopic techniques and represented a rare example of a synthetic FeIV(OH) complex. The reaction of 1 with the one-electron oxidizing agent was reported to form a ligand-oxidized FeIII(OH) complex (2). 3 revealed a one-electron reduction potential of -0.22 V vs Fc+/Fc at -15 °C, which was 150 mV anodically shifted than 2 (Ered = -0.37 V vs Fc+/Fc at -15 °C), inferring 3 to be more oxidizing than 2. 3 reacted spontaneously with (4-OMe-C6H4)3C• to form (4-OMe-C6H4)3C(OH) through rebound of the OH group and displayed significantly faster reactivity than 2. Further, activation of the hydrocarbon C-H and the phenolic O-H bond by 2 and 3 was compared and showed that 3 is a stronger oxidant than 2. A detailed kinetic study established the occurrence of a concerted proton-electron transfer/hydrogen atom transfer reaction of 3. Studying one-electron reduction of 2 and 3 using decamethylferrocene (Fc*) revealed a higher ket of 3 than 2. The study established that the primary coordination sphere around Fe and the redox state of the metal center is very crucial in controlling the reactivity of high-valent Fe-OH complexes. Further, a FeIII(OMe) complex (4) was synthesized and thoroughly characterized, including X-ray structure determination. The reaction of 4 with PhINTs resulted in the formation of a FeIV(OMe) species (5), revealing the presence of two FeIV species with isomer shifts of -0.11 mm/s and = 0.17 mm/s in the Mössbauer spectrum and showed FeIV/FeIII potential at -0.36 V vs Fc+/Fc couple in acetonitrile at -15 °C. The reactivity studies of 5 were investigated and compared with the FeIV(OH) complex (3).

Catalytic reduction of oxygen to water by non-heme iron complexes: exploring the effect of the secondary coordination sphere proton exchanging site.

In this study, we prepared non-heme FeIII complexes (1, 2, and 3) of an N4 donor set of ligands (H2L, Me2L, and BPh2L). 1 is supported by a monoanionic bispyridine-dioxime ligand (HL). In 2 and 3, the primary coordination sphere of Fe remained similar to that in 1, except that the oxime protons of the ligand were replaced with two methyl groups and a bridging -BPh2 moiety, respectively. X-ray structures of the FeII complexes (1a and 3a) revealed similar Fe-N distances; however, they were slightly elongated in 2a. The FeIII/FeII potential of 1, 2, and 3 appeared at -0.31 V, -0.25 V, and 0.07 V vs. Fc+/Fc, respectively, implying that HL and Me2L have comparable donor properties. However, BPh2L is more electron deficient than HL or Me2L. 1 showed electrocatalytic oxygen reduction reaction (ORR) activity in acetonitrile in the presence of trifluoroacetic acid (TFAH) as the proton source at Ecat/2 = -0.45 V and revealed selective 4e-/4H+ reduction of O2 to H2O. 1 showed an effective overpotential (ηeff) of 0.98 V and turnover frequency (TOFmax) of 1.02 × 103 s-1. Kinetic studies revealed a kcat of 2.7 × 107 M-2 s-1. Strikingly, 2 and 3 remained inactive for electrocatalytic ORR, which established the essential role of the oxime scaffolds in the electrocatalytic ORR of 1. Furthermore, a chemical ORR of 1 has been investigated using decamethylferrocene as the electron source. For 1, a similar rate equation was noted to that of the electrocatalytic pathway. A kcat of 6.07 × 104 M-2 s-1 was found chemically. Complex 2, however, underwent a very slow chemical ORR. Complex 3 chemically enhances the 4e-/4H+ reduction of O2 and exhibits a TOF of 0.24 s-1 and a kcat value of 2.47 × 102 M-1 s-1. Based on the experimental observations, we demonstrate that the oxime backbone of the ligand in 1 works as a proton exchanging site in the 4e-/4H+ reduction of O2. The study describes how the ORR is affected by the tuning of the ligand scaffold in a family of non-heme Fe complexes.

Understanding the Effect of Internal Electrostatic Fields Created by Alkaline Earth Metal Ions Poised over Secondary Coordination Sphere of Molecular Iron Complexes.

Understanding the effect of the local electrical field around the reaction center in enzymes and molecular catalysis is an important topic of research. Herein, we explored the electrostatic field exerted by the alkaline earth metal ions (M2+ = Mg2+, Ca2+, Sr2+, and Ba2+) around Fe in FeIII(Cl) complexes by experimental and computational investigations. M2+ coordinated dinuclear FeIII(Cl) complexes (12M) were synthesized and characterized by X-ray crystallography and different spectroscopic techniques. EPR and magnetic moment measurements exhibited the presence of high-spin FeIII centers in the 12M complexes. Electrochemical investigations revealed FeIII/FeII reduction potential values shifted anodically in 12M complexes compared to 1. Likewise, 2p3/2 and 2p1/2 peaks in the XPS data were found to shift positively in the 12M complexes, demonstrating that redox-inactive metal ions make FeIII more electropositive. However, nearly similar λmax values in the UV-vis spectra were observed in 1 and 12M complexes. The first-principles-based computational simulations further revealed the impact of M2+ on stabilizing 3d-orbitals of Fe. The distortion in Laplacian distribution (∇2ρ(r)) of electron density around M2+ also indicates the possibility of having Fe-M interactions in these complexes. The absence of a bond critical point between FeIII and M2+ ions in the 12M complexes indicates dominant through-space interaction between these metal centers. Experimental and computational studies collectively imply that the installation of internal electrostatic fields exerted by M2+ ions in 12M complexes alters the electronic structure of FeIII.

Structural and Spectroscopic Characterization of Copper(III) Complexes and Subsequent One-Electron Oxidation Reaction and Reactivity Studies.

The formation of Cu(III) species are often invoked as the key intermediate in Cu-catalyzed organic transformation reactions. In this study, we synthesized Cu(II) (1) and Cu(III) (3) complexes supported by a bisamidate-bisalkoxide ligand consisting of an ortho-phenylenediamine (o-PDA) scaffold and characterized them through an array of spectroscopic techniques, including UV-visible, electron paramagnetic resonance, X-ray crystallography, and 1H nuclear magnetic resonance (NMR) and X-ray absorption spectroscopy. The Cu-N/O bond distances in 3 are ∼0.1 Šreduced compared to 1, implying a significant increase in 3's overall effective nuclear charge. Further, a Cu(III) complex (4) of a bisamidate-bisalkoxide ligand containing a trans-cyclohexane-1,2-diamine moiety exhibits nearly identical Cu-N/O bond distances to that of 3, inferring that the redox-active o-PDA backbone is not oxidized upon one-electron oxidation of the Cu(II) complex (1). In addition, a considerable difference in the 1s → 4p and 1s → 3d transition energy was observed in the X-ray absorption near-edge structure data of 3 vs 1, which is typical for the metal-centered oxidation process. Electrochemical measurements of the Cu(II) complex (1) in acetonitrile exhibited two consecutive redox couples at -0.9 and 0.4 V vs the Fc+/Fc reference electrode. One-electron oxidation reaction of 3 further resulted in the formation of a ligand-oxidized Cu complex (3a), which was characterized in depth. Reactivity studies of species 3 and 3a were explored toward the activation of the C-H/O-H bonds. A bond dissociation free energy (BDFE) value of ∼69 kcal/mol was estimated for the O-H bond of the Cu(II) complex formed upon transfer of hydrogen atom to 3. The study represents a thorough spectroscopic characterization of high-valent Cu complexes and sheds light on the PCET reactivity studies of Cu(III) complexes.

Effect of Redox-Inactive Metal Ion-Nickel(III) Interactions on the Redox Properties and Proton-Coupled Electron Transfer Reactivity.

Mononuclear nickel(II) and nickel(III) complexes of a bisamidate-bisalkoxide ligand, (NMe4)2[NiII(HMPAB)] (1) and (NMe4)[NiIII(HMPAB)] (2), respectively, have been synthesized and characterized by various spectroscopic techniques including X-ray crystallography. The reaction of redox-inactive metal ions (Mn+ = Ca2+, Mg2+, Zn2+, Y3+, and Sc3+) with 2 resulted in 2-Mn+ adducts, which was assessed by an array of spectroscopic techniques including X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and reactivity studies. The X-ray structure of Ca2+ coordinated to Ni(III) complexes, 2-Ca2+T, was determined and exhibited an average Ni-Ca distance of 3.1253 Å, close to the metal ions' covalent radius. XAS analysis of 2-Ca2+ and 2-Y3+ in solution further revealed an additional coordination to Ca and Y in the 2-Mn+ adducts with shortened Ni-M distances of 2.15 and 2.11 Å, respectively, implying direct bonding interactions between Ni and Lewis acids (LAs). Such a short interatomic distance between Ni(III) and M is unprecedented and was not observed before. EPR analysis of 2 and 2-Mn+ species, moreover, displayed rhombic signals with gav > 2.12 for all complexes, supporting the +III oxidation state of Ni. The NiIII/NiII redox potential of 2 and 2-Mn+ species was determined, and a plot of E1/2 of 2-Mn+ versus pKa of [M(H2O)n]m+ exhibited a linear relationship, implying that the NiIII/NiII potential of 2 can be tuned with different redox-inactive metal ions. Reactivity studies of 2 and 2-Mn+ with different 4-X-2,6-ditert-butylphenol (4-X-DTBP) and other phenol derivatives were performed, and based on kinetic studies, we propose the involvement of a proton-coupled electron transfer (PCET) pathway. Analysis of the reaction products after the reaction of 2 with 4-OMe-DTBP showed the formation of a Ni(II) complex (1a) where one of the alkoxide arms of the ligand is protonated. A pKa value of 24.2 was estimated for 1a. The reaction of 2-Mn+ species was examined with 4-OMe-DTBP, and it was observed that the k2 values of 2-Mn+ species increase by increasing the Lewis acidity of redox-inactive metal ions. However, the obtained k2 values for 2-Mn+ species are much lower compared to the k2 value for 2. Such a variation of PCET reactivity between 2 and 2-Mn+ species may be attributed to the interactions between Ni(III) and LAs. Our findings show the significance of the secondary coordination sphere effect on the PCET reactivity of Ni(III) complexes and furnish important insights into the reaction mechanism involving high-valent nickel species, which are frequently invoked as key intermediates in Ni-mediated enzymatic reactions, solar-fuel catalysis, and biomimetic/synthetic transformation reactions.