Iron(II) complexes with amide-containing macrocycles as non-heme porphyrin analogues

Iron(II) complexes of macrocyclic pentadendate ligands 3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),14,16-triene-2,13-dione (H2pydioneN5) and 16-chloro-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),14,16-triene-2,13-dione (H2pyCldioneN5) were synthesized and fully characterized. Complexes with one or two deprotonated amide groups of H2pydione were both isolated. In the former case the metal ion has a distorted octahedral coordination sphere; in the latter case the complex adopts a pentagonal-bipyramidal geometry. NMR experiments show that the protonation state of the ligand is preserved in a dimethyl sulfoxide (DMSO) solution. The complexes maintain a high-spin state even at low temperatures. Detailed kinetic studies of oxygenation of the iron(II) complexes showed that the deprotonation state of the complex has a profound effect on the reactivity with dioxygen. Oxygenation of the dideprotonated complex of iron(II), Fe(pydioneN5), in aprotic solvents proceeds via a path that is analogous to that of iron(II) porphyrins: via iron(III) superoxo and diiron(III) peroxo species, as evidenced by the spectral changes during the reaction, which is second-order in the concentration of the iron(II) complex, and with an inverse dependence of the reaction rate on the concentration of dioxygen. The final products of oxygenation are crystallographically characterized iron(III) mu-oxo dimers. We have also found that the presence of 1-methylimidazole stabilizes the diiron peroxo intermediate. The reaction of Fe(pydioneN5) with dioxygen in methanol is distinctly different under the same conditions. The reaction is first-order in both iron(II) complex and dioxygen, and no intermediate is spectroscopically observed. Similar behavior was observed for the monodeprotonated complex Fe(HpydioneN5)(Cl). The presence of an accessible proton either from the solvent (reactions in methanol) or from the complex itself (in Fe(HpydioneN5)(Cl)) proves sufficient to alter the oxygenation pathway in these macrocyclic systems, which is reminiscent of the properties of iron(II) porphyrin complexes. The new amidopyridine macrocycles can be considered as new members of the "expanded porphyrin analogue" family. The expansion of the cavity provides control over the spin state and availability of protons. These macrocyclic systems also allow for easy synthetic modifications, paving the way to new, versatile metal complexes.     

Aerobic catechol oxidation catalyzed by a bis(mu-oxo)dimanganese(III,III) complex via a manganese(II)-semiquinonate complex

A 3,5-di-tert-butyl-1,2-semiquinonato (DTBSQ) adduct of Mn(II) was prepared by a reaction between Mn(II)(TPA)Cl(2) (TPA = tris(pyridin-2-ylmethyl)amine) and DTBSQ anion and was isolated as a tetraphenylborate salt. The X-ray crystal structure revealed that the complex is formulated as a manganese(II)-semiquinonate complex [Mn(II)(TPA)(DTBSQ)](+) (1). The electronic spectra in solution also indicated the semiquinonate coordination to Mn. The exposure of 1 in acetonitrile to dioxygen afforded 3,5-di-tert-butyl-1,2-benzoquione and a bis(mu-oxo)dimanganese(III,III) complex [Mn(III)(2)(mu-oxo)(2)(TPA)(2)](2+) (2). The reaction of 2 with 3,5-di-tert-butylcatechol (DTBCH(2)) quantitatively afforded two equivalents of 1 under anaerobic conditions. The highly efficient catalytic oxidation of DTBCH(2) with dioxygen was achieved by combining the above two reactions, that is, by constructing a catalytic cycle involving both manganese complexes 1 and 2. It was revealed that dioxygen is reduced to water but not to hydrogen peroxide in the catalytic cycle.     

Redox properties of NN′-X-phenylenebis(Y-salicyli-deneiminato)iron(II) complexes and reactivity of the corresponding iron(III) complexes towards catecholates

The electrochemical behaviour of a series of iron(II) complexes with the tetradentate ligand NN′-1,2-phenylenebis(salicylideneimine), [Fe(II)L], was studied in non-aqueous solvents. The redox properties of the complexes were related to the nature of the substituents in the aromatic rings. Attention was devoted to dioxygen reactivity of the complexes. The electrode activity of the catechol—[NN′-1,2-phenylenebis(salicylidene-iminato) iron(III)] system, [Fe(III)L(catH)], was also studied; the results gave evidence that both the electrochemical oxidation and the chemical oxidation by dioxygen of [Fe(II)L] in the presence of catechol lead to the complex [Fe(III)L(catH)].     

Oxygen activation by nonheme iron(II) complexes: alpha-keto carboxylate versus carboxylate

Mononuclear iron(II) alpha-keto carboxylate and carboxylate compounds of the sterically hindered tridentate face-capping ligand Tp(Ph2) (Tp(Ph2) = hydrotris(3,5-diphenylpyrazol-1-yl)borate) were prepared as models for the active sites of nonheme iron oxygenases. The structures of an aliphatic alpha-keto carboxylate complex, [Fe(II)(Tp(Ph2))(O(2)CC(O)CH(3))], and the carboxylate complexes [Fe(II)(Tp(Ph2))(OBz)] and [Fe(II)(Tp(Ph2))(OAc)(3,5-Ph(2)pzH)] were determined by single-crystal X-ray diffraction, all of which have five-coordinate iron centers. Both the alpha-keto carboxylate and the carboxylate compounds react with dioxygen resulting in the hydroxylation of a single ortho phenyl position of the Tp(Ph2) ligand. The oxygenation products were characterized spectroscopically, and the structure of the octahedral iron(III) phenolate product [Fe(III)(Tp(Ph2))(OAc)(3,5-Ph(2)pzH)] was established by X-ray diffraction. The reaction of the alpha-keto carboxylate model compounds with oxygen to produce the phenolate product occurs with concomitant oxidative decarboxylation of the alpha-keto acid. Isotope labeling studies show that (18)O(2) ends up in the Tp(Ph2) phenolate oxygen and the carboxylate derived from the alpha-keto acid. The isotope incorporation mirrors the dioxygenase nature of the enzymatic systems. Parallel studies on the carboxylate complexes demonstrate that the oxygen in the hydroxylated ligand is also derived from molecular oxygen. The oxygenation of the benzoylformate complex is demonstrated to be first order in metal complex and dioxygen, with activation parameters DeltaH++ = 25 +/- 2 kJ mol(-1) and DeltaS++ = -179 +/- 6 J mol(-1) K(-1). The rate of appearance of the iron(III) phenolate product is sensitive to the nature of the substituent on the benzoylformate ligand, exhibiting a Hammett rho value of +1.3 indicative of a nucleophilic mechanism. The proposed reaction mechanism involves dioxygen binding to produce an iron(III) superoxide species, nucleophilic attack of the superoxide at the alpha-keto functionality, and oxidative decarboxylation of the adduct to afford the oxidizing species that attacks the Tp(Ph2) phenyl ring. Interestingly, the alpha-keto carboxylate complexes react 2 orders of magnitude faster than the carboxylate complexes, thus emphasizing the key role that the alpha-keto functionality plays in oxygen activation by alpha-keto acid-dependent iron enzymes.     

Effects of thioether substituents on the O2 reactivity of beta-diketiminate-Cu(I) complexes: probing the role of the methionine ligand in copper monooxygenases

The activation of dioxygen by dopamine beta-monooxygenase (DbetaM) and peptidylglycine alpha-hydroxylating monooxygenase (PHM) is postulated to occur at a copper site ligated by two histidine imidazoles and a methionine thioether, which is unusual because such thioether ligation is not present in other O2-activating copper proteins. To assess the possible role of the thioether ligand in O2 activation by DbetaM and PHM, two new ligands comprising beta-diketiminates with thioether substituents were synthesized and Cu(I) and Cu(II) complexes were isolated. The Cu(II) compounds are monomeric and exhibit intramolecular thioether coordination. While the Cu(I) complexes exhibit a multinuclear topology in the solid state, variable-temperature 1H NMR studies implicate equilibria in solution, possibly including monomers with intramolecular thioether coordination that are structurally defined by DFT calculations. Low-temperature oxygenation of solutions of the Cu(I) complexes generates stable 1:1 Cu/O2 adducts, which on the basis of combined experimental and theoretical studies adopt side-on "eta(2)" structures with negligible Cu-thioether bonding and significant peroxo-Cu(III) character. In contrast to previously reported findings with related ligands lacking the thioether group, however (cf., Aboelella; et al. J. Am. Chem. Soc. 2004, 126, 16896), purging the solutions of the thioether-containing adducts with argon results in conversion to bis(mu-oxo)dicopper(III) species. A role for the thioether in promoting loss of O2 from the 1:1 Cu/O2 adduct and facilitating trapping of the resulting Cu(I) complex to yield the bis(mu-oxo) species is proposed, and the possible relevance of this role to that of the methionine in the active sites of DbetaM and PHM is discussed.     

Reaction of (mu-oxo)diiron(III) core with CO2 in N-methylimidazole: formation of mono(mu-carboxylato)(mu-oxo)diiron(III) complexes with N-methylimidazole as ligands

Several iron(III) complexes with N-methylimidazole (N-MeIm) as the ligand have been synthesized by using N-MeIm as the solvent. Under anaerobic conditions, [Fe(N-MeIm)(6)](ClO(4))(3) (1) reacts with stoichiometric amounts of water in N-MeIm to afford the (mu-oxo)diiron(III) complex, [Fe(2)(mu-O)(N-MeIm)(10)](ClO(4))(4) (3). Exposure of a solution of 3 in N-MeIm to stoichiometric and excess CO(2) gives rise to the (mu-oxo)(mu-carboxylato)diiron(III) species [Fe(2)(mu-O)(mu-HCO(2))(N-MeIm)(8)](ClO(4))(3) (4) and the methyl carbonate complex [Fe(2)(mu-O)(mu-CH(3)OCO(2))(N-MeIm)(8)](ClO(4))(3) (5), respectively. Formation of the formato-bridged complex 4 upon fixation of CO(2) by 3 in N-MeIm is unprecedentated. Methyl transfer from N-MeIm to a bicarbonato-bridged (mu-oxo)diiron(III) intermediate appears to give rise to 5. Complex 3 is a good starting material for the synthesis of (mu-oxo)mono(mu-carboxylato)diiron(III) species [Fe(2)(mu-O)(mu-RCO(2))(N-MeIm)(8)](ClO(4))(3) (where R = H (4), CH(3) (6), or C(6)H(5) (7)); addition of the respective carboxylate ligand in stoichiometric amount to a solution of 3 in N-MeIm affords these complexes in high yields. Attempts to add a third bridge to complexes 4, 6, and 7 to form the (mu-oxo)bis(mu-carboxylato)diiron(III) species result in the isolation of the previously known triiron(III) mu-eta(3)-oxo clusters [[Fe(mu-RCO(2))(2)(N-MeIm)](3)O](ClO(4)) (8). The structures of 3, 4, 6, and 7 allow one, for the first time, to inspect the various features of the [Fe(2)(mu-O)(mu-RCO(2))](3+) moiety with no strain from the ligand framework.     

Correlation of spin states and spin delocalization with the dioxygen reactivity of catecholatoiron(III) complexes

A series of catecholatoiron(III) complexes, [Fe(III)L(4Cl-cat)]BPh4 (L = (4-MeO)2TPA (1), TPA (2), (4-Cl)2TPA (3), (4-NO2)TPA (4), (4-NO2)2TPA (5); TPA = tris(pyridin-2-ylmethyl)amine; 4Cl-cat = 4-chlorocatecholate), have been characterized by magnetic susceptibility measurements and EPR, 1H NMR, and UV-vis-NIR spectroscopies to clarify the correlation of the spin delocalization on the catecholate ligand with the O2 reactivity as well as the spin-state dependence of the O2 reactivity. EPR spectra in frozen CH3CN at 123 K clearly showed that introduction of electron-withdrawing groups effectively shifts the spin equilibrium from a high-spin to a low-spin state. The effective magnetic moments determined by the Evans method in a CH3CN solution showed that 5 contains 36% of low-spin species at 243 K, while 1-4 are predominantly in a high-spin state. Evaluation of spin delocalization on the 4Cl-cat ligand by paramagnetic 1H NMR shifts revealed that the semiquinonatoiron(II) character is more significant in the low-spin species than in the high-spin species. The logarithm of the reaction rate constant is linearly correlated with the energy gap between the catecholatoiron(III) and semiquinonatoiron(II) states for the high-spin complexes 1-3, although complexes 4 and 5 deviate negatively from linearity. The lower reactivity of the low-spin complex, despite its higher spin density on the catecholate ligand compared with the high-spin analogues, suggests the involvement of the iron(III) center, rather than the catecholate ligand, in the reaction with O2.     

Formation, characterization, and reactivity of bis(mu-oxo)dinickel(III) complexes supported by a series of bis[2-(2-pyridyl)ethyl]amine ligands.

Bis(mu-oxo)dinickel(III) complexes supported by a series of bis[2-(2-pyridyl)ethyl]amine ligands have been successfully generated by treating the corresponding bis(mu-hydroxo)dinickel(II) complexes or bis(mu-methoxo)dinickel(II) complex with an equimolar amount of H(2)O(2) in acetone at low temperature. The bis(mu-oxo)dinickel(III) complexes exhibit a characteristic UV-vis absorption band at approximately 410 nm and a resonance Raman band at 600-610 cm(-1) that shifted to 570-580 cm(-1) upon (18)O-substitution. Kinetic studies and isotope labeling experiments using (18)O(2) imply the existence of intermediate(s) such as peroxo dinickel(II) in the course of formation of the bis(mu-oxo)dinickel(III) complex. The bis(mu-oxo)dinickel(III) complexes supported by the mononucleating ligands (L1(X) = para-substituted N,N-bis[2-(2-pyridyl)ethyl]-2-phenylethylamine; X = OMe, Me, H, Cl) gradually decompose, leading to benzylic hydroxylation of the ligand side arm (phenethyl group). The kinetics of the ligand hydroxylation process including kinetic deuterium isotope effects (KIE), p-substituent effects (Hammett plot), and activation parameters (Delta H(H)(*) and Delta S(H)(*)) indicate that the bis(muxo)dinickel(III) complex exhibits an ability of hydrogen atom abstraction from the substrate moiety as in the case of the bis(mu-oxo)dicopper(III) complex. Such a reactivity of bis(mu-oxo)dinickel(III) complexes has also been suggested by the observed reactivity toward external substrates such as phenol derivatives and 1,4-cyclohexadiene. The thermal stability of the bis(mu-oxo)dinickel(III) complex is significantly enhanced when the dinucleating ligand with a longer alkyl strap is adopted instead of the mononucleating ligand. In the m-xylyl ligand system, no aromatic ligand hydroxylation occurred, showing a sharp contrast with the reactivity of the (mu-eta(2):eta(2)-peroxo)dicopper(II) complex with the same ligand which induces aromatic ligand hydroxylation via an electrophilic aromatic substitution mechanism. Differences in the structure and reactivity of the active oxygen complexes between the nickel and the copper systems are discussed on the basis of the detailed comparison of these two systems with the same ligand.     

Kinetic analysis of the conversion of nonheme (alkylperoxo)iron(III) species to iron(IV) complexes

Low-spin mononuclear (alkylperoxo)iron(III) complexes decompose by peroxide O-O bond homolysis to form iron(IV) species. We examined the kinetics of previously reported homolysis reactions for (alkylperoxo)iron(III) intermediates supported by TPA (tris(2-pyridylmethyl)amine) in CH3CN solution and promoted by pyridine N-oxide, and by BPMCN (N,N-bis(2-pyridylmethyl)-N,N-dimethyl-trans-1,2-diaminocyclohexane) in its cis-beta configuration in CH3CN and CH2Cl2, as well as for the previously unreported chemistry of TPA and 5-Me3TPA intermediates in acetone. Each of these reactions forms an oxoiron(IV) complex, except for the beta-BPMCN reaction in CH2Cl2 that yields a novel (hydroxo)(alkylperoxo)iron(IV) product. Temperature-dependent rate measurements suggest a common reaction trajectory for each of these reactions and verify previous theoretical estimates of a ca. 60 kJ/mol enthalpic barrier to homolysis. However, both the tetradentate supporting ligand and exogenous ligands in the sixth octahedral coordination site significantly perturb the homolyses, such that observed rates can vary over 2 orders of magnitude at a given temperature. This is manifested as a compensation effect in which increasing activation enthalpy is offset by increasingly favorable activation entropy. Moreover, the applied kinetic model is consistent with geometric isomerism in the low-spin (alkylperoxo)iron(III) intermediates, wherein the alkylperoxo ligand is coordinated in either of the inequivalent cis sites afforded by the nonheme ligands.     

Synthesis, structure, and properties of an Fe(II) carbonyl [(PaPy3)Fe(CO)](ClO4): insight into the reactivity of Fe(II)-CO and Fe(II)-NO moieties in non-heme iron chelates of N-donor ligands

An Fe(II) carbonyl complex [(PaPy3)Fe(CO)](ClO4) (1) of the pentadentate ligand N,N-bis(2-pyridylmethyl)amine-N-ethyl-2-pyridine-2-carboxamide (PaPy3H, H is the dissociable amide proton) has been synthesized and structurally characterized. This Fe(II) carbonyl exhibits its nu(CO) at 1972 cm(-1), and its 1H NMR spectrum in degassed CD3CN confirms its S = 0 ground state. The bound CO in 1 is not photolabile. Reaction of 1 with an equimolar amount of NO results in the formation of the {Fe-NO}7 nitrosyl [(PaPy3)Fe(NO)](ClO4) (2), while excess NO affords the iron(III) nitro complex [(PaPy3)Fe(NO2)](ClO4) (5). In the presence of [Fe(Cp)2]+ and excess NO, 1 forms the {Fe-NO}6 nitrosyl [(PaPy3)Fe(NO)](ClO4)2 (3). Complex 1 also reacts with dioxygen to afford the iron(III) mu-oxo species [{(PaPy3)Fe}2O](ClO4)2 (4). Comparison of the metric and spectral parameters of 1 with those of the previously reported {Fe-NO}6,7 nitrosyls 3 and 2 provides insight into the electronic distributions in the Fe(II)-CO, Fe(II)-NO, and Fe(II)-NO+ bonds in the isostructural series of complexes 1-3 derived from a non-heme polypyridine ligand with one carboxamide group.     

Ligand effect on reversible conversion between copper(I) and bis(mu-oxo)dicopper(III) complex with a sterically hindered tetradentate tripodal ligand and monooxygenase activity of bis(mu-oxo)dicopper(III) complex

A new sterically hindered tetradentate tripodal ligand (Me2-etpy) and its labeled analogue having deuterated methylene groups (d4-Me2-etpy) were synthesized, where Me2-etpy is bis(6-methyl-2-pyridylmethyl)(2-pyridylethyl)amine. Copper(I) complexes [Cu(Me2-etpy or d4-Me2-etpy)]+ (1 and 1-d4, respectively) reacted with dioxygen at -80 degrees C in acetone to give bis(mu-oxo)dicopper(III) complexes [Cu2(O)2(Me2-etpy or d4-Me2-etpy)2](2+) (1-oxo and 1-d4-oxo, respectively), the latter of which was crystallographically characterized. Unlike a bis(mu-oxo)dicopper(III) complex with a closely related Me2-tpa ligand having a 2-pyridylmethyl pendant, 1-oxo possessing a 2-pyridylethyl pendant is not fully formed even under 1 atm of O2 at -80 degrees C and is very reactive toward the oxidation of the supporting ligand. Thermal decomposition of 1-oxo gave an N-dealkylated ligand in yield approximately 80% based on a dimer and a corresponding aldehyde. The deuterated ligand d4-Me2-etpy greatly stabilizes the bis(mu-oxo)dicopper(III) complex 1-d4-oxo, indicating that the rate determining step of the N-dealkylation is the C-H bond cleavage from the methylene group. The reversible conversion between 1-d4 and 1-d4-oxo in acetone is dependent on the temperature, and the thermodynamic parameters (DeltaH and DeltaS) of the equilibrium were determined to be -53 +/- 2 kJ mol(-1) and -187 +/- 10 J mol(-1) K(-1), respectively. The effect of the 2-pyridylethyl pendant in comparison with the 2-pyridylmethyl and 6-methyl-2-pyridylmethyl pendants on the physicochemical properties of the copper(I) and bis(mu-oxo)dicopper(III) species is discussed.     

Topologically constrained manganese(III) and iron(III) complexes of two cross-bridged tetraazamacrocycles

A family of Mn3+ and Fe3+ complexes of 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (1) and 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (2) has been prepared by the chemical oxidation of the divalent manganese and iron analogues. The ligands are ethylene cross-bridged tetraazamacrocycles derived from cylam and cyclen, respectively. The synthesis and characterization of these complexes, including X-ray crystal structure determinations, are described. The structural evidence demonstrates that the tetradentate ligands enforce distorted octahedral geometries on the metal ions, with two cis sites occupied by labile ligands. Magnetic measurements reveal that the complexes are high spin with typical magnetic moments. Cyclic voltammetry shows reversible redox processes for the Fe3+/Fe2+ couples of the iron(III) complexes, while Mn3+/Mn2+ and Mn4+/Mn3+ couples were observed for the complexes with manganese(III). The manganese chemistry of 1 was studied in depth. The dichloro manganese(III) cation of 1 undergoes facile ligand substitution reactions at the labile, monodentate sites, for example substituting azide for chloride ligands. Air oxidation of the dichloro complex of Mn (1)2+ in basic solution does not give the expected mu-oxo dimeric product common to manganese. Instead, an unusual manganese(III)-OH complex has been isolated from this reaction and structurally characterized. A similar reaction under slightly different conditions gives a putative MnIII(OH)2 complex that metathesizes to MnIII(OMe)2 upon recrystallization from methanol.     

Copper dioxygen adducts: formation of bis(mu-oxo)dicopper(III) versus (mu-1,2)Peroxodicopper(II) complexes with small changes in one pyridyl-ligand substituent

The preference for the formation of a particular Cu 2O 2 isomer coming from (ligand)-Cu (I)/O 2 reactivity can be regulated with the steric demands of a TMPA (tris(2-pyridylmethyl)amine) derived ligand possessing 6-pyridyl substituents on one of the three donor groups of the tripodal tetradentate ligand. When this substituent is an -XHR group (X = N or C) the traditional Cu (I)/O 2 adduct forms a (mu-1,2)peroxodicopper(II) species ( A). However, when the substituent is the slightly bulkier XR 2 moiety {aryl or NR 2 (R not equal H)}, a bis(mu-oxo)dicopper(III) structure ( C) is favored. The reactivity of one of the bis(mu-oxo)dicopper(III) species, [{(6tbp)Cu (III)} 2(O (2-)) 2] (2+) ( 7-O 2 ) (6tbp = (6- (t)Bu-phenyl-2-pyridylmethyl)bis(2-pyridylmethyl)amine), was probed, and for the first time, exogenous toluene or ethylbenzene hydrocarbon oxygenation reactions were observed. Typical monooxygenase chemistry occurred: the benzaldehyde product includes an 18-O atom for toluene/ 7- (1) (8)O 2 reactivity, and a H-atom abstraction by 7-O 2 is apparent from study of its reactions with ArOH substrates, as well as the determination of k H/ k D approximately 7 in the toluene oxygenation (i.e., PhCH 3 vs PhCD 3 substrates). Proposed courses of reaction are presented, including the possible involvement of PhCH 2OO (*) and its subsequent reaction with copper(I) complex, the latter derived from dynamic solution behavior of 7-O 2 . External TMPA ligand exchange for copper in 7-O 2 and O-O bond (re)formation chemistry, along with the ability to protonate 7-O 2 and release of H 2O 2 indicate the presence of an equilibrium between [{(6tbp)Cu (III)} 2(O (2-)) 2] (2+) ( 7-O 2 ) and a (mu-1,2)peroxodicopper(II) form.     

Synthesis and characterization of mononuclear ruthenium(III) pyridylamine complexes and mechanistic insights into their catalytic alkane functionalization with m-chloroperbenzoic acid

A series of mononuclear RuIII complexes [RuCl2(L)]+, where L is tris(2-pyridylmethyl)amine (TPA) or one of four TPA derivatives as tetradentate ligand, were prepared and characterized by spectroscopic methods, X-ray crystallography, and electrochemical measurements. The geometry of a RuIII complex having a non-threefold-symmetric TPA ligand bearing one dimethylnicotinamide moiety was determined to show that the nicotine moiety resides trans to a pyridine group, but not to the chlorido ligand. The substituents of the TPA ligands were shown to regulate the redox potential of the ruthenium center, as indicated by a linear Hammett plot in the range of 200 mV for RuIII/RuIV couples with a relatively large rho value (+0.150). These complexes act as effective catalysts for alkane functionalization in acetonitrile with m-chloroperbenzoic acid (mCPBA) as terminal oxidant at room temperature. They exhibited fairly good reactivity for oxidation of cyclohexane (C--H bond energy 94 kcal mol(-1)), and the reactivity can be altered significantly by the electronic effects of substituents on TPA ligands in terms of initial rates and turnover numbers. Catalytic oxygenation of cyclohexane by a RuIII complex with 16O-mCPBA in the presence of H2 18O gave 18O-labeled cyclohexanol with 100% inclusion of the 18O atom from the water molecule. Resonance Raman spectra under catalytic conditions without the substrate indicate formation of a RuIV==O intermediate with lower bonding energy. Kinetic isotope effects (KIEs) in the oxidation of cyclohexane suggest that hydrogen abstraction is the rate-determining step and the KIE values depend on the substituents of the TPA ligands. Thus, the reaction mechanism of catalytic cyclohexane oxygenation depends on the electronic effects of the ligands.     

Synthesis and characterization of an iron(III) complex of glycine derivative of bis(phenol)amine ligand in relevance to catechol dioxygenase active site

A glycine derivative of bis(phenol)amine ligand (HL^Gly) was synthesized and characterized by ¹H NMR and IR spectroscopies. The iron(III) complex (L^GlyFe) of this ligand was synthesized and characterized by IR, UV-Vis, X-ray and magnetic susceptibility studies. X-ray analysis reveals that in L^GlyFe the iron(III) center has a distorted trigonal bipyramidal coordination sphere and is surrounded by an amine nitrogen, a carboxylate and two phenolate oxygen atoms. The mentioned carboxylate group acts as μ-bridging ligand for iron centers of neighbor complexes. The variable-temperature magnetic susceptibility indicates that L^GlyFe is the paramagnetic high spin iron(III) complex. It has been shown that electrochemical oxidation of this complex is ligand-centered due to the oxidation of phenolate to the phenoxyl radicals. The L^GlyFe complex also undergoes an electrochemical metal-centered reduction of ferric to ferrous ion. The oxygenation of 3,5-di-tert-butyl-catechol, with L^GlyFe in the presence of dioxygen was investigated.     

Copper(II) and copper(III) complexes of pyrrole-appended oxacarbaporphyrin

The reaction of an O-confused porphyrin with a pendant pyrrole 4 and copper(II) acetate yields an organocopper(III) diamagnetic complex 4-Cu(III) substituted at the C(3) position by the pyrrole and H. The transformation of 4-Cu(III), performed in aerobic conditions, gave a rare copper(II) organometallic compound 6-Cu(II). In the course of this process, the tetrahedral-trigonal rearrangement originated at the C(3) atom but effects the whole structure. The electron paramagnetic resonance spectroscopic features correspond to a copper(II) oxidation state. A crystallographic analysis of 6-Cu(II) confirmed the formation of a direct metal-C bond [Cu(II)-C 1.939(4) A]. It was found that the Cu(II) complex of O-confused oxaporphyrin is sensitive to oxidative conditions. The degradation of 6-Cu(II) to yield copper(II) tripyrrinone complexes has been observed, which was considered as a peculiar case of dioxygen activation in a porphyrin-like environment. This process is accompanied by regioselective oxygenation at the inner C to form the 2-oxa-3-(2'-pyrrolyl)-21-hydroxycarbaporphyrinatocopper(II) complex ((pyrr)OCPO)CuII (8). The reaction of 6-Cu(II) with hydrogen peroxide, performed under heterophasic conditions, resulted in quantitative regioselective hydroxylation centered at the internal C(21) atom, also producing 8. Treatment of 8 with acid results in demetalation to form the nonaromatic 21-hydroxy O-confused porphyrin derivative ((pyrr)OCPOH)H (9).     

Biomimetic hydrocarbon oxidation catalyzed by nonheme iron(III) complexes with peracids: evidence for an Fe(V)=O species

Mononuclear nonheme iron(III) complexes of tetradentate ligands containing two deprotonated amide moieties, [Fe(Me(2)bpb)Cl(H(2)O)] (3 a) and [Fe(bpc)Cl(H(2)O)] (4 a), were prepared by substitution reactions involving the previously synthesized iron(III) complexes [Et(3)NH][Fe(Me(2)bpb)Cl(2)] (3) and [Et(3)NH][Fe(bpc)Cl(2)] (4). Complexes 3 a and 4 a were characterized by IR and elemental analysis, and complex 3 a also by X-ray crystallography. Nonheme iron(III) complexes 3, 3 a, 4, and 4 a catalyze olefin epoxidation and alcohol oxidation on treatment with m-chloroperbenzoic acid. Pairwise comparisons of the reactivity of these complexes revealed that the nature of the axial ligand (Cl(-) versus H(2)O) influences the yield of oxidation products, whereas an electronic change in the supporting chelate ligand has little effect. Hydrocarbon oxidation by these catalysts was proposed to involve an iron(V) oxo species which is formed on heterolytic O-O bond cleavage of an iron acylperoxo intermediate (FeOOC(O)R). Evidence for this iron(V) oxo species was derived from KIE (k(H)/k(D)) values, H(2) (18)O exchange experiments, and the use of peroxyphenylacetic acid (PPAA) as the peracid. Our results suggest that an Fe(V)=O moiety can form in a system wherein the supporting chelate ligand comprises a mixture of neutral and anionic nitrogen donors. This work is relevant to the chemistry of mononuclear nonheme iron enzymes that are proposed to oxidize organic substrates via reaction pathways involving high-valent iron oxo species.     

Spectroscopic characterization of the oxo-transfer reaction from a bis(mu-oxo)dicopper(III) complex to triphenylphosphine

The oxygen-atom transfer reaction from the bis(mu-oxo)dicopper(III) complex [Cu(III)(2)(mu-O)(2)(L)(2)](2+), where L =N,N,N',N' -tetraethylethylenediamine, to PPh(3) has been studied by UV-vis, EPR, (1)H NMR and Cu K-edge X-ray absorption spectroscopy in parallel at low temperatures (193 K) and above. Under aerobic conditions (excess dioxygen), 1 reacted with PPh(3), giving O=Ph(3) and a diamagnetic species that has been assigned to an oxo-bridged dicopper(II) complex on the basis of EPR and Cu K-edge X-ray absorption spectroscopic data. Isotope-labeling experiments ((18)O(2)) established that the oxygen atom incorporated into the triphenylphosphine oxide came from both complex 1 and exogenous dioxygen. Detailed kinetic studies revealed that the process is a third-order reaction; the rate law is first order in both complex 1 and triphenylphosphine, as well as in dioxygen. At temperatures above 233 K, reaction of 1 with PPh(3) was accompanied by ligand degradation, leading to oxidative N-dealkylation of one of the ethyl groups. By contrast, when the reaction was performed in the absence of excess dioxygen, negligible substrate (PPh(3)) oxidation was observed. Instead, highly symmetrical copper complexes with a characteristic isotropic EPR signal at g= 2.11 were formed. These results are discussed in terms of parallel reaction channels that are activated under various conditions of temperature and dioxygen.     

Facile ring opening of iron(III) and iron(II) complexes of meso-amino-octaethylporphyrin by dioxygen

Pyridine solutions of ClFe(III)(meso-NH(2)-OEP) undergo oxidative ring opening when exposed to dioxygen. The high-spin iron(III) complex, ClFe(III)(meso-NH(2)-OEP), has been isolated and characterized by X-ray crystallography. In the solid state, it has a five-coordinate structure typical for high-spin (S = 5/2) iron(III) complex. In chloroform-d solution, ClFe(III)(meso-NH(2)-OEP) displays an (1)H NMR spectrum characteristic of a high-spin, five-coordinate complex and is unreactive toward dioxygen. However, in pyridine-d(5) solution a temperature-dependent equilibrium exists between the high-spin (S = 5/2), six-coordinate complex, [(py)ClFe(III)(meso-NH(2)-OEP)], and the six-coordinate, low spin (S = 1/2 with the less common (d(xz)d(yz))(4)(d(xy))(1) ground state)) complex, [(py)(2)Fe(III)(meso-NH(2)-OEP)](+). Such pyridine solutions are air-sensitive, and the remarkable degradation has been monitored by (1)H NMR spectroscopy. These studies reveal a stepwise conversion of ClFe(III)(meso-NH(2)-OEP) into an open-chain tetrapyrrole complex in which the original amino group and the attached meso carbon atom have been converted into a nitrile group. Additional oxidation at an adjacent meso carbon occurs to produce a ligand that binds iron by three pyrrole nitrogen atoms and the oxygen atom introduced at a meso carbon. This open-chain tetrapyrrole complex itself is sensitive to attack by dioxygen and is converted into a tripyrrole complex that is stable to further oxidation and has been isolated. The process of oxidation of the Fe(III) complex, ClFe(III)(meso-NH(2)-OEP), is compared with that of the iron(II) complex, (py)(2)Fe(II)(meso-NH(2)-OEP); both converge to form identical products.     

The coordination chemistry of FeCl3 and FeCl2 to bis[2-(2,3-dihydroxyphenyl)-6-pyridylmethyl](2-pyridylmethyl)amine: access to a diiron(III) compound with an unusual pentagonal-bipyramidal/square-pyramidal environment

Coordination of FeCl3 to the title ligand yields a mononuclear iron(III) complex 1, which was characterized by spectroscopic techniques and X-ray diffraction. The ligand is (kappa3-N) tridentate and the metal, which lies in a pseudo-octahedral environment, is bound to a phenolate group from the catechol substituent. The dichloroiron(II) complex 2 was easily obtained by metalation of the ligand with FeCl2 and characterized by various spectroscopic techniques. In their cyclic voltammograms both 1 and 2 display the same reversible FeII/FeIII wave at E1/2=10 mV (vs. SCE). Reduction of compound 1 with Zn/Hg yields 2', which displays identical properties to 2. Taken together, these findings indicate that in spite of the different oxidation state of the metal in 2, no major geometrical/structural change is observed at the metal center with respect to 1. The reaction of 2 with dioxygen in the absence of organic substrates proceeds extremely rapidly and yields compound 3, which is a diiron(III) derivative whose X-ray crystal structure is also reported. The possibility of a radical-based mechanism is discussed. Compound 3 displays an unusual geometry: one iron(III) center is seven-coordinate, whereas the other lies in a square-pyramidal environment. The two iron atoms are bridged by the catecholato substituents. To the best of our knowledge, 3 is the first example of a seven-coordinate iron(III) derivative with tris(2-pyridylmethyl)amine ligands.