Phenolic Bond Research Articles

Introducing NH2 onto polymeric films via photo-induced C—H bond transformation with phenol derivatives as building blocks

A one-step process to introduce both the aromatic and aliphatic primary amino groups with high chemoselectivity was developed. Triplet state acetone abstracts the hydrogen atoms from both the C-H bond of the polymeric film substrate and the O-H bond of phenol which is the building block and the amino group carrier. As a result, two kinds of free radicals, confined carbon-centered chain radicals of the polymer substrate and mobile oxygen-centered phenoxy radicals, were generated. Then the C-O bonds were formed by the coupling reaction between these two kinds of free radicals. p-Tyramine and p-aminophenol were used as amino carriers. The successful introduction of amino groups onto LDPE, BOPP and PET film substrates was demonstrated by measurements of water contract angle (CA), ultraviolet spectra (UV), X-ray photoelectron spectroscopy (XPS) and fluorescent microscopy. The processing factors, such as the UV-light intensity and irradiation time, concentrations of p-tyramine and p-aminophenol, and the ratio of acetone/water were investigated. The optimized process parameters are as follows: UV light intensity 9500 μW/cm2; irradiation time 18 min for BOPP and LDPE, 22 min for PET; the ratio of acetone/water = 1; and concentration of p-tyramine and p-aminophenol 15% for BOPP and LDPE, 1% for PET. Based on the UV absorbance, the amino groups on the polymeric substrates were estimated to be in the range of 6.3 × 10-6–9.5 × 10-6 mmol/mm2.

Vibrational energy redistribution in catechol during ultraviolet photolysis

This article reports the striking interplay between the molecular structure and the photodissociation dynamics of catechol (a key dihydroxybenzene), identified using a combination of electronic spectroscopy, hydrogen (Rydberg) atom photofragment translational spectroscopy, density functional theory and second order approximate coupled cluster methods. We describe how the non-planar (C(1) symmetry) ← planar (C(s) symmetry) geometry change during S(1) (1(1)ππ*) ←S(0) excitation in catechol, as well as the presence of internal hydrogen bonding, can perturb the photodissociation dynamics relative to that of phenol (a monohydroxybenzene), particularly with respect to O-H bond fission via the lowest dissociative (1)πσ* state. For λ(phot) > 270 nm, O-H bond fission (of the non hydrogen bonded hydroxyl moiety) is deduced to proceed via H atom tunnelling from the photo-prepared 1(1)ππ* state into the lowest (1)πσ* state of the molecule. The vibrational energy distribution in the resulting catechoxyl product changes notably as λ(phot) is tuned on resonance with either the v' = 0, m(2)' = 1(+) or m(2)' = 2(+) torsional levels of the photo-prepared 1(1)ππ* state: the product state distribution is highly sensitive to the degree of OH torsional excitation (m(2)) prepared during photo-excitation. It is deduced that such torsional excitation can be redistributed very efficiently into ring puckering (and likely also in-plane ring stretch) vibrations as the molecule tunnels to its repulsive 1(1)πσ* state and dissociates. These observations can be rationalised by consideration of the photo-prepared nuclear wavefunctions. Analysis of the product vibrational energy distribution also reveals that the O-H bond strength of the non hydrogen bonded O-H moiety in catechol, D(0)(H-catechoxyl) ≤ 27 480 ± 50 cm(-1), ∼2500 cm(-1) lower than that of the sole O-H bond in bare phenol. As a consequence, the vertical excitation energy of the 1(1)πσ* state in catechol is reduced relative to that in phenol, yielding a particularly broad distribution of product vibrations for λ(phot) < 270 nm. This study highlights the interplay between molecular geometry and redistribution of vibrational energy during ultraviolet photolysis of phenols.

Effects of solvent polarity on the reaction of phenol with tolylene‐2,4‐diisocyanate

AbstractUsing tolylene‐2,4‐diisocyanate as standard compound, the relationship between NCO absorbance and concentration was studied with in situ FTIR. The linear relationship appeared correct only for concentrations lower than 0.4 mol L−1. Then, the urethane reaction kinetics of phenol with tolylene‐2,4‐diisocyanate were investigated in different solvents, such as dimethyl sulfoxide, cyclohexanone, n‐butyl acetate, 1,4‐dioxane, and xylene. It showed that solvents largely affected reaction rates. The reaction was largely accelerated in polar solvents, following the order of dimethyl sulfoxide &gt; cyclohexanone &gt; n‐butyl acetate &gt; 1,4‐dioxane &gt; xylene. It was in contrast to the alcohol–diisocyanate reaction. Finally, an appropriate reaction mechanism was proposed. The HO bond in phenol was polarized under the influence of solvents, which made the combination of hydrogen to nitrogen and alkoxyl group to carbenium easier. After that the solvent was dissociated and the carbamate generated. The kinetic equation could be derived as v = k′K·[S:] [ROH]·[R′NCO]. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Theoretical study on the unimolecular decomposition of thiophenol

The potential energy surface for the unimolecular decomposition of thiophenol (C(6)H(5)SH) is mapped out at two theoretical levels; BB1K/GTlarge and QCISD(T)/6-311+G(2d,p)//MP2/6-31G(d,p). Calculated reaction rate constants at the high pressure limit indicate that the major initial channel is the formation of C(6)H(6)S at all temperatures. Above 1000 K, the contribution from direct fission of the S-H bond becomes important. Other decomposition channels, including expulsion of H(2) and H(2)S are of negligible importance. The formation of C(6)H(6)S is predicted to be strong-pressure dependent above 900 K. Further decomposition of C(6)H(6)S produces CS and C(5)H(6). Overall, despite the significant difference in bond dissociation, i.e., 8-9 kcal/mol between the S-H bond in thiophenol and the O-H bond in phenol, H migration at the ortho position in the two molecules represents the most accessible initial channel.

Effect of Coal Structure on Mechanical and Thermal Properties of Coal Filled Soy Protein Composites

Using different rank coals as filler, coal-soy protein isolate (SPI) composites were prepared by compression molding processing using glycerol as plasticizer. The structure of the coals used were characterized by Fourier transform infrared (FTIR), ultimate analysis, and surface functional group analysis. The effects of coal structure on the mechanical properties, water resistance, and thermal properties were investigated. The results showed that, in different rank coals, the atomic ratio of oxygen to carbon, carboxylic acid groups, phenolic hydroxyl groups, lactone bonds, and aliphatic chains decreased with coal rank. The strength, water resistance, and glass transition temperature of coal-SPI composites decreased with coal rank. Lower ran coal filler with more reactive functional groups caused the composites strong but brittle. While, higher rank coals provide poor mechanical properties for the composites.

Oxidovanadium(IV) Schiff Base Complex Derived from Vitamin B6: Synthesis, Characterization, and Insulin Enhancing Properties

A new Schiff base, [H(4)pydmedpt](2+)·2Cl(-), derived from one of the forms of vitamin B(6) has been synthesized by condensation of pyridoxal hydrochloride with N,N-bis[3-aminopropyl]-methylamine (medpt) and characterized by analytical and spectroscopic methods. The molecular structure is calculated by density functional theory (DFT) procedures, and the donor properties of each individual donor atom are evaluated by calculation of the Fukui function. One pot reaction of pyridoxal and medpt with vanadyl acetylacetonate yields the brown complex [V(IV)O(H(2)pydmedpt)](2+)·2Cl(-)1, which upon recrystallization from water crystallizes as [V(IV)O(pydmedpt)]·5H(2)O 2. The compounds are characterized by analytical and spectroscopic methods, 2 being also characterized by single crystal X-ray diffraction. It displays a slightly distorted octahedral geometry around the vanadium atom involving the coordination of N(amine), two N(imine), and O(phenolato) donors of the ligand. One of the phenolato oxygen donors is positioned trans to the terminal O-oxido atom with relatively short V-O(phenolate) {2.041(3) Å} and long V-O(oxido) {1.625(4) Å} bond distances when compared to other known compounds. The two different pK(a) values (6.0 and 7.9) obtained for 1 are due to protonation of the pyridine ring nitrogen atoms having different basic characters, this being also substantiated by theoretical calculation of the proton affinity of the O- and N- atoms of the molecule. The spin Hamiltonian parameters are obtained from the electron paramagnetic resonance (EPR) spectra, but the A(z) value (ca. 155 × 10(-4) cm(-1)) is lower than expected by applying the additivity rule for the present set of equatorial donor atoms (ca. 162-163 × 10(-4) cm(-1)), this being attributed to the strong trans V-O(phenolate) bond. The UV-vis transitions and EPR spectral parameters are calculated by DFT procedures, and both the calculated electronic transitions and the hyperfine coupling constants agree well with those experimentally observed. The inhibitory effect of 1 on FFA release and % glucose uptake determined with isolated rat adipocyte cells gave IC(50) and EC(50) values lower than for V(IV)OSO(4) and of the same order of magnitude of other reported insulin enhancing vanadium compounds.

Regulating function of alkali metal on the strength of OH⋯O hydrogen bond in phenol–water complex: Weak to strong and strong to weak

Quantum chemical calculations have been performed for the complexes of phenol and M-substituted phenol (M = Li, Na, K) with water to investigate the regulating function of the M atom on the strength of OH⋯O hydrogen bond. The results show that the presence of the M atom in the phenol ring enhances the hydrogen bond with water as the proton donor but weakens the hydrogen bond with water as the proton acceptor. The regulating effect of alkali metal confirms to the order of Li < Na < K. Natural bond orbital and aims in molecules analyses have been carried out to unveil the regulating mechanism of the M atom. It is demonstrated that the M effect is realized through the hyperconjugation and electrostatic induction interactions.

Spectro-electrochemical and DFT studies of a planar Cu(II)–phenolate complex active in the aerobic oxidation of primary alcohols

A square-planar compound [Cu(pyrimol)Cl] (pyrimol=4-methyl-2-N-(2-pyridylmethylene)aminophenolate) abbreviated as CuL–Cl) is described as a biomimetic model of the enzyme galactose oxidase (GOase). This copper(II) compound is capable of stoichiometric aerobic oxidation of activated primary alcohols in acetonitrile/water to the corresponding aldehydes. It can be obtained either from Hpyrimol (HL) or its reduced/hydrogenated form Hpyramol (4-methyl-2-N-(2-pyridylmethyl)aminophenol; H2L) readily converting to pyrimol (L−) on coordination to the copper(II) ion. Crystalline CuL–Cl and its bromide derivative exhibit a perfect square-planar geometry with Cu–O(phenolate) bond lengths of 1.944(2) and 1.938(2)Å. The cyclic voltammogram of CuL–Cl exhibits an irreversible anodic wave at +0.50 and +0.57V versus ferrocene/ferrocenium (Fc/Fc+) in dry dichloromethane and acetonitrile, respectively, corresponding to oxidation of the phenolate ligand to the corresponding phenoxyl radical. In the strongly donating acetonitrile the oxidation path involves reversible solvent coordination at the Cu(II) centre. The presence of the dominant CuII–L chromophore in the electrochemically and chemically oxidised species is evident from a new fairly intense electronic absorption at 400–480nm ascribed to a several electronic transitions having a mixed π→π∗(L) intraligand and Cu–Cl→L charge transfer character. The EPR signal of CuL–Cl disappears on oxidation due to strong intramolecular antiferromagnetic exchange coupling between the phenoxyl radical ligand (L) and the copper(II) centre, giving rise to a singlet ground state (S=0). The key step in the mechanism of the primary alcohol oxidation by CuL–Cl is probably the α-hydrogen abstraction from the equatorially bound alcoholate by the phenoxyl moiety in the oxidised pyrimol ligand, Cu–L, through a five-membered cyclic transition state.

Bis{2-methoxy-6-[(4-methylphenyl)iminiomethyl]phenolato-κ2O1,O2}tris(nitrato-κ2O,O′)methanolsamarium(III)

The asymmetric unit of the title compound, [Sm(NO3)3(C15H15NO2)2(CH3OH)], contains two Schiff base 2-meth­oxy-6-[(4-methyl­phen­yl)iminiometh­yl]phenolate (HL) ligands, three nitrate ions and one methanol mol­ecule that binds to the nine-coordinate samarium(III) ion via its O atoms. The HL ligands chelate with a strong Sm—O(deprotonated phenolic) bond and a weak Sm—O(meth­oxy) contact. The latter can be inter­preted as the apices of the bicapped square-anti­prismatic SmIIIO9 polyhedron. The Schiff base ligands are in a zwitterionic state with the phenolic H atom transferred to the imine N atom. O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds lend stability to the structure. One O atom of one nitrate group is equally disordered over two positions.

Effect of surfactants on the chemiluminescence of acridinium dimethylphenyl ester labels and their conjugates

Chemiluminescent acridinium dimethylphenyl esters, containing two methyl groups flanking the phenolic ester bond, display excellent chemiluminescence stability and are used as labels in automated immunoassays for clinical diagnostics. Light emission from these labels is triggered with alkaline peroxide in the presence of the cationic surfactant cetyltrimethylammonium chloride. Under these conditions, light emission is rapid and is complete in <5 s. In the present study we examined the effect of various surfactants on light emission from acridinium dimethylphenyl ester labels and their conjugates containing hydrophilic linkers derived either from hexa(ethylene)glycol or a sulfobetaine zwitterion. Sulfobetaine zwitterions are very polar and incorporation of these functional groups in acridinium dimethyphenyl esters and their conjugates represents a new approach to improving the aqueous solubility of these chemiluminescent labels. Our results indicate that in general, surfactants affect light emission from these labels and their conjugates by two discrete mechanisms. Cationic surfactants, but not anionic or non-ionic surfactants, accelerate overall light emission kinetics and a more modest effect is observed with zwitterionic surfactants. Surfactants also enhance total light output and the magnitude of this enhancement is maximal for cationic surfactants and a sulfobetaine zwitterionic surfactant. These observations are the first to clearly delineate the role of the surfactant on the chemiluminescence reaction pathway of acridinium esters and can be rationalized based on known effects of surfactant aggregates on bimolecular and unimolecular reactions.

Quantum-chemical DFT calculations of the energies of the O—H bond of phenols

The energies of homolytic cleavage of the O—H bonds in 36 phenols with various structures were calculated within the scope of density functional theory using a series of exchange-correlation functionals and basis sets. The best agreement between the calculated and experimental data is given by the M06-2X/6-311++G(2d,2p)//B3LYP/6-31G(d) method.

Bis{6-methoxy-2-[(4-methylphenyl)iminiomethyl]phenolate-κ2O,O′}tris(nitrato-κ2O,O′)holmium(III) monohydrate

The crystal structure of the title compound, [Ho(NO3)3(C15H15NO2)2]·H2O, contains two Schiff base 6-meth­oxy-2-[(4-methyl­phen­yl)iminiometh­yl]phenolate (L) ligands, three independent nitrate ions that chelate to the HoIII ion with O atoms and a hydrate water mol­ecule. The coordination environment of the HoIII ion is ten-coordinate. The L ligands chelate with a strong Ho—O(phenolate) bond and weaker Ho—O(meth­oxy) contacts. The latter can be inter­preted as the apices of the bicapped square–anti­prismatic [HoO10] polyhedron. Inter­molecular N—H⋯O hydrogen bonds occur. Intra­molecular O—H⋯O inter­actions link the complex mol­ecules and uncoordinated water mol­ecules.

Electronic Structure and Spectro-Structural Correlations of FeIIIZnII Biomimetics for Purple Acid Phosphatases: Relevance to DNA Cleavage and Cytotoxic Activity

Purple acid phosphatases (PAPs) are a group of metallohydrolases that contain a dinuclear Fe(III)M(II) center (M(II) = Fe, Mn, Zn) in the active site and are able to catalyze the hydrolysis of a variety of phosphoric acid esters. The dinuclear complex [(H(2)O)Fe(III)(μ-OH)Zn(II)(L-H)](ClO(4))(2) (2) with the ligand 2-[N-bis(2-pyridylmethyl)aminomethyl]-4-methyl-6-[N'-(2-pyridylmethyl)(2-hydroxybenzyl) aminomethyl]phenol (H(2)L-H) has recently been prepared and is found to closely mimic the coordination environment of the Fe(III)Zn(II) active site found in red kidney bean PAP (Neves et al. J. Am. Chem. Soc. 2007, 129, 7486). The biomimetic shows significant catalytic activity in hydrolytic reactions. By using a variety of structural, spectroscopic, and computational techniques the electronic structure of the Fe(III) center of this biomimetic complex was determined. In the solid state the electronic ground state reflects the rhombically distorted Fe(III)N(2)O(4) octahedron with a dominant tetragonal compression aligned along the μ-OH-Fe-O(phenolate) direction. To probe the role of the Fe-O(phenolate) bond, the phenolate moiety was modified to contain electron-donating or -withdrawing groups (-CH(3), -H, -Br, -NO(2)) in the 5-position. The effects of the substituents on the electronic properties of the biomimetic complexes were studied with a range of experimental and computational techniques. This study establishes benchmarks against accurate crystallographic structural information using spectroscopic techniques that are not restricted to single crystals. Kinetic studies on the hydrolysis reaction revealed that the phosphodiesterase activity increases in the order -NO(2) ←Br ←H ←CH(3) when 2,4-bis(dinitrophenyl)phosphate (2,4-bdnpp) was used as substrate, and a linear free energy relationship is found when log(k(cat)/k(0)) is plotted against the Hammett parameter σ. However, nuclease activity measurements in the cleavage of double stranded DNA showed that the complexes containing the electron-withdrawing -NO(2) and electron-donating -CH(3) groups are the most active while the cytotoxic activity of the biomimetics on leukemia and lung tumoral cells is highest for complexes with electron-donating groups.

Bis{[6-methoxy-2-(4-methylphenyl)iminiomethyl]phenolate-κ2O,O′}tris(nitrato-κ2O,O′)europium(III)

The crystal structure of title compound, [Eu(NO3)3(C15H15NO2)2], contains two Schiff base 6-meth­oxy-2-[(4-methyl­phen­yl)imino­meth­yl]phenolate (L) ligands and three independent nitrate ions that chelate to the europium(III) ion via the O atoms. The coordination number of the EuIII ion is ten. The L ligands chelate with a strong Eu—O(deprotonated phenolate) bond and a weak Eu—O(meth­oxy) contact, the latter can be inter­preted as the apices of the bicapped square-anti­prismatic EuIII polyhedron. Intra­molecular N—H⋯O hydrogen bonds occur.

Lactosylamidine-based affinity purification for cellulolytic enzymes EG I and CBH I from Hypocrea jecorina and their properties

Selective adsorption and separation of β-glucosidase, endo-acting endo-β-(1→4)-glucanase I (EG I), and exo-acting cellobiohydrolase I (CBH I) were achieved by affinity chromatography with β-lactosylamidine as ligand. A crude cellulase preparation from Hypocrea jecorina served as the source of enzyme. When crude cellulase was applied to the lactosylamidine-based affinity column, β-glucosidase appeared in the unbound fraction. By contrast, EG I and CBH I were retained on the column and then separated from each other by appropriately adjusting the elution conditions. The relative affinities of the enzymes, based on their column elution conditions, were strongly dependent on the ligand. The highly purified EG I and CBH I, obtained by affinity chromatography, were further purified by Mono P and DEAE chromatography, respectively. EG I and CBH I cleave only at the phenolic bond in p-nitrophenyl glycosides with lactose and N-acetyllactosamine (LacNAc). By contrast, both scissile bonds in p-nitrophenyl glycosides with cellobiose were subject to hydrolysis although with important differences in their kinetic parameters.

ChemInform Abstract: Spin Polarization in 1,3,5‐Trihydroxybenzene‐Bridged First‐Row Transition Metal Complexes

AbstractReview: 125 refs.

Aqua{6,6′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}methanolmanganese(III)) perchlorate hemihydrate

The asymmetric unit of the title compound, [Mn(C18H18N2O4)(CH3OH)(H2O)]ClO4·0.5H2O, contains two complex cations and two perchlorate anions, one of which is disordered over two positions in a 0.767 (8):0.233 (8) ratio. The MnIII atoms are in distorted octa­hedral environments. In addition to the equatorial tetra­dentate salicylaldimine ligand, each Mn is axially coordinated by both a methanol and a water mol­ecule. The complex is a dimer held together by multiple strong and weak hydrogen-bonding inter­actions between the coordinated water mol­ecule on one monomer with all the phenolic and meth­oxy O atoms on the other monomer. In addition, the two perchlorate anions are linked by hydrogen bonds to the two methanol mol­ecules coordinated to each Mn center. The Mn—O phenolic bond distances range from 1.868 (2) to 1.882 (2) Å while the Mn—N distances range from 1.978 (2) to 1.981 (2) Å. Mn—O distances for the axial water and methanol ligands are longer at 2.226 (2)/2.257 (2) and 2.313 (2)/2.324 (2) Å, reflecting the usual Jahn–Teller distortion as found in MnIII complexes.

Influence of “Remote” Intramolecular Hydrogen Bonds on the Stabilities of Phenoxyl Radicals and Benzyl Cations

Remote intramolecular hydrogen bonds (HBs) in phenols and benzylammonium cations influence the dissociation enthalpies of their O-H and C-N bonds, respectively. The direction of these intramolecular HBs, para --> meta or meta --> para, determines the sign of the variation with respect to molecules lacking remote intramolecular HBs. For example, the O-H bond dissociation enthalpy of 3-methoxy-4-hydroxyphenol, 4, is about 2.5 kcal/mol lower than that of its isomer 3-hydroxy-4-methoxyphenol, 5, although group additivity rules would predict nearly identical values. In the case of 3-methoxy-4-hydroxybenzylammonium and 3-hydroxy-4-methoxybenzylammonium ions, the CBS-QB3 level calculated C-N eterolytic dissociation enthalpy is about 3.7 kcal/mol lower in the former ion. These effects are caused by the strong electron-withdrawing character of the -O(*) and -CH(2)(+) groups in the phenoxyl radical and benzyl cation, respectively, which modulates the strength of the HB. An O-H group in the para position of ArO(*) or ArCH(2)(+) becomes more acidic than in the parent molecules and hence forms stronger HBs with hydrogen bond acceptors (HBAs) in the meta position. Conversely, HBAs, such as OCH(3), in the para position become weaker HBAs in phenoxyl radicals and benzyl cations than in the parent molecules. These product thermochemistries are reflected in the transition states for, and hence in the kinetics of, hydrogen atom abstraction from phenols by free radicals (dpph(*) and ROO(*)). For example, the 298 K rate constant for the 4 + dpph(*) reaction is 22 times greater than that for the 5 + dpph(*) reaction. Fragmentation of ring-substituted benzylammonium ions, generated by ESI-MS, to form the benzyl cations reflects similar remote intramolecular HB effects.

Theoretical investigation of the hydrogen bonding interaction between substituted phenols and simple O- and N-bases

The hydrogen bond interaction between substituted phenols (X = NH 2, CH 3, H, Cl, CN, NO 2) and O-bases (HOF, H 2O, CH 3OH, (CH 3) 2O) or N-bases (NHF 2, NH 2F, NH 3, CH 3NH 2) is investigated theoretically at the B3LYP/6-31++G(d,p) level. The calculations include the optimized geometries, the interaction energies, the frequency shifts of the ν(OH) stretching vibration along with relevant NBO parameters such as the charges on the atoms, the occupation of antibonding orbitals and the second-order hyperconjugation energies. The role of both the deprotonation enthalpies of the proton donor O–H bonds of phenols and the proton affinities of the O- or N-bases are explored. The differences between the OH⋯O and OH⋯N hydrogen bonds are outlined.

Novel square pyramidal iron(iii) complexes of linear tetradentate bis(phenolate) ligands as structural and reactive models for intradiol-cleaving 3,4-PCD enzymes: Quinone formation vs. intradiol cleavage

The iron(iii) complexes of the bis(phenolate) ligands 1,4-bis(2-hydroxy-4-methyl-benzyl)-1,4-diazepane H(2)(L1), 1,4-bis(2-hydroxy-4-nitrobenzyl)-1,4-diazepane H(2)(L2), 1,4-bis(2-hydroxy-3,5-dimethylbenzyl)-1,4-diazepane H(2)(L3) and 1,4-bis(2-hydroxy-3,5-di-tert-butylbenzyl)-1,4-diazepane H(2)(L4) have been isolated and studied as structural and functional models for 3,4-PCD enzymes. The complexes [Fe(L1)Cl] 1, [Fe(L2)(H(2)O)Cl] 2, [Fe(L3)Cl] 3 and [Fe(L4)Cl] 4 have been characterized using ESI-MS, elemental analysis, and absorption spectral and electrochemical methods. The single crystal X-ray structure of 3 contains the FeN(2)O(2)Cl chromophore with a novel square pyramidal (τ, 0.20) coordination geometry. The Fe-O-C bond angle (135.5°) and Fe-O bond length (1.855 Å) are very close to the Fe-O-C bond angles (133, 148°) and Fe-O(tyrosinate) bond distances (1.81, 1.91 Å) in 3,4-PCD enzyme. All the complexes exhibit two intense absorption bands in the ranges 335-383 and 493-541 nm, which are assigned respectively to phenolate (pπ) → Fe(iii) (dσ*) and phenolate (pπ) → Fe(iii) (dπ*) LMCT transitions. The Fe(iii)/Fe(ii) redox potentials of 1, 3 and 4 (E(1/2), -0.882--1.010 V) are more negative than that of 2 (E(1/2), -0.577 V) due to the presence of two electron-withdrawing p-nitrophenolate moieties in the latter enhancing the Lewis acidity of the iron(iii) center. Upon adding H(2)DBC pretreated with two equivalents of Et(3)N to the iron(iii) complexes, two catecholate-to-iron(iii) LMCT bands (656, ε, 1030; 515 nm, ε, 1330 M(-1) cm(-1)) are observed for 2; however, interestingly, an intense catecholate-to-iron(iii) LMCT band (530-541 nm) is observed for 1, 3 and 4 apart from a high intensity band in the range 451-462 nm. The adducts [Fe(L)(DBC)](-) generated from 1-4in situ in DMF/Et(3)N solution react with dioxygen to afford almost exclusively the simple two-electron oxidation product 3,5-di-tert-butylbenzoquinone (DBQ), which is discerned from the appearance and increase in intensity of the electronic spectral band around 400 nm, and smaller amounts of cleavage products. Interestingly, in DMF/piperidine the amount of quinone product decreases and those of the cleavage products increase illustrating that the stronger base piperidine enhances the concentration of the catecholate adduct. The rates of both dioxygenation and quinone formation observed in DMF/Et(3)N solution vary in the order 1 > 3 > 4 < 2 suggesting that the ligand steric hindrance to molecular oxygen attack, the Lewis acidity of the iron(iii) center and the ability of the complexes to rearrange the Fe-O phenolate bonds to accommodate the catecholate substrate dictate the extent of interaction of the complexes with substrate and hence determine the rates of reactions. This is in line with the observation of DBSQ/H(2)DBC reduction wave for the adduct [Fe(L2)(DBC)](-) at a potential (E(1/2): -0.285 V) more positive than those for the adducts of 1, 3 and 4 (E(1/2): -0.522 to -0.645 V).