Electronic structure of six-coordinate iron(III) monoazaporphyrins

The electronic structures of six-coordinate iron(III) octaethylmonoazaporphyrins, [Fe(MAzP)L 2] (+/-) ( 1), have been examined by means of (1)H NMR and EPR spectroscopy to reveal the effect of meso-nitrogen in the porphyrin ring. The complexes carrying axial ligands with strong field strengths such as 1-MeIm, DMAP, CN (-), and (t)BuNC adopt the low-spin state with the (d xy ) (2)(d xz , d yz ) (3) ground state in a wide temperature range where the (1)H NMR and EPR spectra are taken. In contrast, the complexes with much weaker axial ligands, such as 4-CNPy and 3,5-Cl 2Py, exhibit the spin transition from the mainly S = 3/2 at 298 K to the S = 1/2 with the (d xy ) (2)(d xz , d yz ) (3) ground state at 4 K. Only the THF complex has maintained the S = 3/2 throughout the temperature range examined. Thus, the electronic structures of 1 resemble those of the corresponding iron(III) octaethylporphyrins, [Fe(OEP)L 2] (+/-) ( 2). A couple of differences have been observed, however, in the electronic structures of 1 and 2. One of the differences is the electronic ground state in low-spin bis( (t)BuNC) complexes. While [Fe(OEP)( (t)BuNC) 2] (+) adopts the (d xz , d yz ) (4)(d xy ) (1) ground state, like most of the bis( (t)BuNC) complexes reported previously, [Fe(MAzP)( (t)BuNC) 2] (+) has shown the (d xy ) (2)(d xz , d yz ) (3) ground state. Another difference is the spin state of the bis(3,5-Cl 2Py) complexes. While [Fe(OEP)(3,5-Cl 2Py) 2] (+) has maintained the mixed S = 3/2 and 5/2 spin state from 298 to 4 K, [Fe(MAzP)(3,5-Cl 2Py) 2] (+) has shown the spin transition mentioned above. These differences have been ascribed to the narrower N4 cavity and the presence of lower-lying pi* orbital in MAzP as compared with OEP.     

Spin density distribution in five- and six-coordinate iron(II)-porphyrin NO complexes evidenced by magnetic circular dichroism spectroscopy

Using magnetic circular dichroism (MCD) spectroscopy together with DFT calculations, the spin density distributions in five-coordinate [Fe(TPP)(NO)] (I) and six-coordinate [Fe(TPP)(MI)(NO)] (II, MI = 1-methylimidazole) are defined. In the five-coordinate complex, a strong Fe-NO sigma bond between pi(*)(h) and d(z)(2) is present that leads to a large transfer of spin density from the NO ligand to Fe(II) corresponding to an electronic structure with noticeable Fe(I)-NO(+) character. Consequently, the MCD spectrum is dominated by paramagnetic C-term contributions. On coordination of the sixth ligand, the spin density is pushed back from the iron toward the NO ligand, resulting in an Fe(II)-NO(radical) type of electronic structure. This is reflected by the fact that the MCD spectrum is dominated by diamagnetic contributions.     

Spectroscopic properties and electronic structure of five- and six-coordinate iron(II) porphyrin NO complexes: Effect of the axial N-donor ligand

In this paper, the differences in the spectroscopic properties and electronic structures of five- and six-coordinate iron(II) porphyrin NO complexes are explored using [Fe(TPP)(NO)] (1; TPP = tetraphenylporphyrin) and [Fe(TPP)(MI)(NO)] (2; MI = 1-methylimidazole) type systems. Binding of N-donor ligands in axial position trans to NO to five-coordinate complexes of type 1 is investigated using UV-vis absorption and 1H NMR spectroscopies. This way, the corresponding binding constants Keq are determined and the 1H NMR spectra of 1 and 2 are assigned for the first time. In addition, 1H NMR allows for the determination of the degree of denitrosylation in solutions of 1 with excess base. The influence of the axial ligand on the properties of the coordinated NO is then investigated. Vibrational spectra (IR and Raman) of 1 and 2 are presented and assigned using isotope substitution and normal-coordinate analysis. Obtained force constants are 12.53 (N-O) and 2.98 mdyn/A (Fe-NO) for 1 compared to 11.55 (N-O) and 2.55 mdyn/A (Fe-NO) for 2. Together with the NMR results, this provides experimental evidence that binding of the trans ligand weakens the Fe-NO bond. The principal bonding schemes of 1 and 2 are very similar. In both cases, the Fe-N-O subunit is strongly bent. Donation from the singly occupied pi* orbital of NO into d(z2) of iron(II) leads to the formation of an Fe-NO sigma bond. In addition, a medium-strong pi back-bond is present in these complexes. The most important difference in the electronic structures of 1 and 2 occurs for the Fe-NO sigma bond, which is distinctively stronger for 1 in agreement with the experimental force constants. The increased sigma donation from NO in 1 also leads to a significant transfer of spin density from NO to iron, as has been shown by magnetic circular dichroism (MCD) spectroscopy in a preceding Communication (Praneeth, V. K. K.; Neese, F.; Lehnert, N. Inorg. Chem. 2005, 44, 2570-2572). This is confirmed by the 1H NMR results presented here. Hence, further experimental and computational evidence is provided that complex 1 has noticeable Fe(I)NO+ character relative to 2, which is an Fe(II)NO(radical) complex. Finally, using MCD theory and quantum chemical calculations, the absorption and MCD C-term spectra of 1 and 2 are assigned for the first time.     

Electronic structure analysis of iron(III)-porphyrin complexes by X-ray absorption spectra at the C, N and Fe K-edges.

X-ray absorption near edge structure (XANES) measurements at the C, N, and Fe K absorption edges were performed for iron(III)-tetraphenylporphyrin (FeTPP), iron(III)-tetrakis(p-carboxyphenyl)porphyrin (FeTCPP), and iron(III)-tetrakis(p-sulfonatophenyl)porphyrin (FeTSPP). The spectral shapes differ in the Fe K XANES, but not in C and N K XANES among FeTPP, FeTCPP, and FeTSPP. Crosschecks of XANES data for C, N, and Fe K absorption edges in combination with discrete variational (DV)-Xalpha molecular orbital (MO) calculations indicate that each p-electron-withdrawing group on four meso-phenyl substitutes in an Fe(III)-porphyrin complex brings about a unique electron state through the complex because of the electron-withdrawal strength, itself. Consequently, they affect the positive charge of the center Fe(III) ion.     

Control of electronic structure of a six-coordinate iron(III) porphyrin radical by means of axial ligands

Addition of tert-butylisocyanide (tBuNC) to a CD2Cl2 solution of the bis(perchlorato)(meso-tetramesitylporphyrinato) iron(III) cation radical leads to the formation of the corresponding bis(adduct), [Fe(TMP)(tBuNC)2]2+, whose electronic structure is in sharp contrast to that of the corresponding imidazole(HIm) complex, [Fe(TMP)(HIm)2]2+; the former adopts the S = 0 while the latter exhibits the S = 1 electronic ground state.     

Electronic structure of adducts of Nd(III) carboxylate complexes determined by DFT and XPS methods

X-ray photoelectron spectroscopy and quantum chemistry methods are used to study Nd(tol)₃ and Nd(сor)₃ carboxylate complexes and their adducts with 1,10-phenanthroline (Nd(tol)₃Phen and Nd(сor)₃Phen₂). The electronic structure and specific features of the nature of chemical bonds are studied, as well as the effect of 1,10-phenanthroline on the electronic structure of the adduct. We propose the band assignment of the valence band of the XPS spectra of all compounds.     

Symmetry and bonding in metalloporphyrins. A modern implementation for the bonding analyses of five- and six-coordinate high-spin iron(III)-porphyrin complexes through density functional calculation and NMR spectroscopy

Bonding interactions between the iron and the porphyrin macrocycle of five- and six-coordinate high-spin iron(III)-porphyrin complexes are analyzed within the framework of approximate density functional theory with the use of the quantitative energy decomposition scheme in combination with removal of the vacant pi orbitals of the porphyrin from the valence space. Although the relative extent of the iron-porphyrin interactions can be evaluated qualitatively through the spin population and orbital contribution analyses, the bond strengths corresponding to different symmetry representations can be only approximated quantitatively by the orbital interaction energies. In contrast to previous suggestions, there are only limited Fe --> P pi back-bonding interactions in high-spin iron(III)-porphyrin complexes. It is the symmetry-allowed bonding interaction between d(z)2 and a(2u) orbitals that is responsible for the positive pi spin densities at the meso-carbons of five-coordinate iron(III)-porphyrin complexes. Both five- and six-coordinate complexes show significant P --> Fe pi donation, which is further enhanced by the movement of the metal toward the in-plane position for six-coordinate complexes. These bonding characteristics correlate very well with the NMR data reported experimentally. The extraordinary bonding interaction between d(z)2 and a(2u) orbitals in five-coordinate iron(III)-porphyrin complexes offers a novel symmetry-controlled mechanism for spin transfer between the axial ligand sigma system and the porphyrin pi system and may be critical to the electron transfer pathways mediated by hemoproteins.     

Electronic structure of bispidine iron(IV) oxo complexes

The electronic structure, based on DFT calculations, of a range of FeIV=O complexes with two tetra- (L1 and L2) and two isomeric pentadentate bispidine ligands (L3 and L4) is discussed with special emphasis on the relative stability of the two possible spin states (S = 1, triplet, intermediate-spin, and S = 2, quintet, high-spin; bispidines are very rigid diazaadamantane-derived 3,7-diazabicyclo[3.3.1]nonane ligands with two tertiary amine and two or three pyridine donors, leading to cis-octahedral [(X)(L)FeIV=O]2+ complexes, where X = NCCH3, OH2, OH-, and pyridine, and where X = pyridine is tethered to the bispidine backbone in L3, L4). The two main structural effects are a strong trans influence, exerted by the oxo group in both the triplet and the quintet spin states, and a Jahn-Teller-type distortion in the plane perpendicular to the oxo group in the quintet state. Due to the ligand architecture the two sites for substrate coordination in complexes with the tetradentate ligands L1 and L2 are electronically very different, and with the pentadentate ligands L3 and L4, a single isomer is enforced in each case. Because of the rigidity of the bispidine ligands and the orientation of the "Jahn-Teller axis", which is controlled by the sixth donor X, the Jahn-Teller-type distortion in the high-spin state of the two isomers is quite different. It is shown how this can be used as a design principle to tune the relative stability of the two spin states.     

Transition-metal chemistry of oxime-containing ligands—XXVII. Five- and six-coordinate complexes of iron(II) and iron(III) with 2,6-diacetylpyridine

Iron(II) and iron(III) complexes of 2,6-diacetylpyridine dioxime (H₂dapd) have been prepared and their electronic and structural properties investi     

Interaction of poly(vinyl acetate) radical with iron (III) complexes

The polymerization of vinyl acetate in N,N-dimethylformamide (DMF) at 60°C initiated by AIBN in the presence of [Fe(DMF)₆](ClO₄)₃ and Fe(N₃)₃ had been studied. Fe(N₃)₃ was produced in situ by mixing solid sodium azide (NaN₃) and hexakis(N,N-dimethylformamide) iron (III) perchlorate, [Fe(DMF)₆](ClO₄)₃, in the ratio of 3:1. The velocity constant k_x for the interaction of poly(vinyl acetate) radical with [Fe(DMF)₆]³⁺ was found to be 1.44 × 10³L mol^?1 s^?1 and that for the interaction of poly(vinyl acetate) radical with Fe(N₃)₃ to be 3.44 × 10⁵ L mol^?1 s^?1 at 60°C.     

An integrated approach to the mid-spin state (S = 3/2) in six-coordinate iron(III) chiroporphyrins

An intermediate-spin state very close to the mid-spin state (S = 3/2) can be stabilized in a ferric porphyrin by an integrated approach which combines the favorable effects of a weak axial field strength and of a small macrocycle hole. Axial ligand exchange by reaction of chloroiron(III)tetramethylchiroporphyrin [(TMCP)FeCl] with silver perchlorate in ethanol-chloroform leads to ethanol-ligated ferric chiroporphyrins. Two distinct crystalline products containing a bisethanol complex [[(TMCP)FeIII(EtOH)2]ClO4] and three variants of a mixed ethanol-water complex [[(TMCP)FeIII(EtOH)(H2O)]ClO4] have been structurally characterized in the solid state. The small hole of the ruffled chiroporphyrin and the weak axial oxygen ligation result in strongly tetragonally distorted complexes. The six-coordinate species exhibit long axial Fe-O bond distances (2.173(5)-2.272(4) A) and the shortest equatorial Fe-N(av) distances (1.950(5)-1.978(7) A) found as yet in a ferric porphyrin, reflecting a singly occupied dz2 orbital and a largely depopulated dx2-y2 orbital. An intriguing case of bond-stretch isomerism is seen for the axial Fe-O bonds in two crystallographically independent mixed ethanol-water species, and it is accounted for by their distinct intra- and intermolecular hydrogen-bond arrays. The M?ssbauer spectrum (delta = 0.35(1) mm s-1 and delta EQ = 3.79(1) mm s-1 at 77 K) indicates a strong tetragonal distortion around the ferric ion, in agreement with the structural data. The value of the magnetic moment (mu eff = 3.8 mu B in the range 50-300 K) strongly supports a mid-spin state (S = 3/2). The EPR spectrum at 80 K (g perpendicular approximately 4.0, g parallel approximately 2.00) is consistent with a nearly pure mid-spin state (4A2) with little rhombic distortion. The 1H NMR spectra in CDCl3-EtOH exhibit upfield-shifted resonances for the pyrrole protons (delta approximately -30 ppm) which are consistent with the depopulated iron dx2-y2 orbital. Solution equilibria with water and various alcohols, and the spin state of the corresponding species, are discussed on the basis of the NMR data. The bisethanol and ethanol-water species are potential models of unknown hemoprotein ligation states such as Tyr(OH)/Tyr(OH) or Tyr(OH)/H2O that could be obtained by site-directed mutagenesis.     

Electronic structure of high-spin iron(III)-alkylperoxo complexes and its relation to low-spin analogues: reaction coordinate of O-O bond homolysis.

The spectroscopic properties of the high-spin Fe(III)-alkylperoxo model complex [Fe(6-Me(3)TPA)(OH(x))(OO(t)Bu)](x)(+) (1; TPA = tris(2-pyridylmethyl)amine, (t)Bu = tert-butyl, x = 1 or 2) are defined and related to density functional calculations of corresponding models in order to determine the electronic structure and reactivity of this system. The Raman spectra of 1 show four peaks at 876, 842, 637, and 469 cm(-1) that are assigned with the help of normal coordinate analysis, and corresponding force constants have been determined to be 3.55 mdyn/A for the O-O and 2.87 mdyn/A for the Fe-O bond. Complex 1 has a broad absorption feature around 560 nm that is assigned to a charge-transfer (CT) transition from the alkylperoxo to a t(2g) d orbital of Fe(III) with the help of resonance Raman profiles and MCD spectroscopy. An additional contribution to the Fe-O bond arises from a sigma interaction between and an e(g) d orbital of iron. The electronic structure of 1 is compared to the related low-spin model complex [Fe(TPA)(OH(x))(OO(t)Bu)](x)(+) and the reaction coordinate for O-O homolysis is explored for both the low-spin and the high-spin Fe(III)-alkylperoxo systems. Importantly, there is a barrier for homolytic cleavage of the O-O bond on the high-spin potential energy surface that is not present for the low-spin complex, which is therefore nicely set up for O-O homolysis. This is reflected by the electronic structure of the low-spin complex having a strong Fe-O and a weak O-O bond due to a strong Fe-O sigma interaction. In addition, the reaction coordinate of the Fe-O homolysis has been investigated, which is a possible decay pathway for the high-spin system, but which is thermodynamically unfavorable for the low-spin complex.     

Molecular structures and magnetic resonance spectroscopic investigations of highly distorted six-coordinate low-spin iron(III) porphyrinate complexes.

Three bis-axially ligated complexes of iron(III) octaethyltetraphenylporphyrin, (OETPP)Fe(III), have been prepared, which are low-spin complexes, each with two axial nitrogen-donor ligands (N-methylimidazole (N-MeIm), 4-(dimethylamino)pyridine (4-NMe(2)Py), and 2-methylimidazole (2-MeImH)). The crystal and molecular structure of the bis-(2-MeImH) complex shows the macrocycle to be in a saddled conformation, with the ligands in perpendicular planes aligned at 14 degrees to the porphyrin nitrogens so as to relieve the steric interaction between the 2-methyl groups and the porphyrin. The Fe-N(por) bond lengths are typical of nonplanar six-coordinate low-spin Fe(III) complexes, while the axial Fe-N(ax) bond lengths are substantially longer than those of [(TPP)Fe(2-MeImH)(2)](+) (2.09(2) A as compared to 2.015(4) and 2.010(4) A). The crystal and molecular structure of the bis-(4-NMe(2)Py) complex also shows the macrocycle to be in a mainly saddled conformation, but with a significant ruffled component. As a result, the average Fe-N(por) bonds are significantly shorter (1.951 A as compared to 1.974 A) than those of the bis-(2-MeImH) complex. One ligand is aligned at 9 degrees to two trans porphyrin nitrogens, while the other is at 79 degrees to the same porphyrin nitrogens, producing a dihedral angle of 70 degrees between the ligand planes. The EPR spectrum of this complex, like that of the bis-(2-MeImH) complex, is of the "large g(max)" type, with g(max) = 3.29 and 3.26, respectively. However, in frozen CD(2)Cl(2), [(OETPP)Fe(N-MeIm)(2)](+) exhibits both "large g(max)" and normal rhombic signals, suggesting the presence of both "perpendicular" and "parallel" ligand orientations. The 1- and 2D (1)H NMR spectra of each of these complexes, as well as the chloroiron(III) starting material, were investigated as a function of temperature. The COSY and NOESY/EXSY spectra of the chloride complex are consistent with the expected J-coupling and saddle inversion dynamics, respectively. Complete spectral assignments for the bis-(N-MeIm) and -(4-NMe(2)Py) complexes have been made using 2D (1)H NMR techniques. In each case, the number of resonances due to methylene (two) and phenyl protons (one each) is consistent with D(2)(d)() symmetry, and therefore an effective perpendicular orientation of the axial ligands on the time scale of the NMR experiments. The temperature dependences of the (1)H resonances of these complexes show significant deviations from Curie behavior, and also evidence of extensive ligand exchange and rotation. Spectral assignment of the eight methylene resonances of the bis-(2-MeImH) complex to the four ethyl groups was possible through the use of 2D (1)H NMR techniques. The complex is fluxional, even at -90 degrees C, and ROESY data suggest that the predominant process is saddle inversion accompanied by simultaneous rotation of the axial ligands. Saddle inversion becomes slow on the 2D NMR time scale as the temperature is lowered in the ligand order of N-MeIm > 4-NMe(2)Py > 2-MeImH, probably due mainly to progressive destabilization of the ground state rather than progressive stabilization of the transition state of the increasingly "hindered" bis-ligand complexes.     

The structure of iron(III) complexes with carbamide derivatives

Infrared spectra of new iron(III) complexes with urea derivatives: [Fe (CH₃HNCONH₂)₆]X₃; [Fe(C₂H₅HNCONH₂)₆]X₃ and [Fe(CH₃-HNCONHCH₃)₆]X₃ (where X = Cl^?, NO^?₃ or $\text{1}\text{2}$SO^2?₄) have been recorded and their interpretation given. The analysis of the infrared spectra was based on a comparison of the positions of bands corresponding to the vibrations of characteristic groups appearing in the complexes and the free ligands. Comparison and analysis of the data show that the urea derivatives coordinate with mono- and disubstituted iron(III) through the oxygen atom of the carbonyl group.     

Cyclometallated ruthenium(III) complexes: Synthesis,structure and properties

Reactions of Schiff bases (H₂apahR) derived from acetophenone and acid hydrazides, triethylamine and [Ru(PPh₃)₃Cl₂] (1:2:1 mole ratio) in methanol provide cyclometallated ruthenium(III) complexes of formula trans-[Ru(apahR)(PPh₃)₂Cl] in 74–81% yields. The complexes have been characterized by elemental analysis, magnetic susceptibility, spectroscopic (infrared, electronic and EPR) and electrochemical measurements. X-ray crystal structures of two representative complexes have been determined. In each complex, the metal centre is in distorted octahedral CNOClP₂ coordination sphere assembled by the C,N,O-donor meridionally spanning apahR^2?, the chloride and the two mutually trans-oriented PPh₃ molecules. All the complexes are one-electron paramagnetic (μ_eff. = 1.85–1.98 μ_B) and display rhombic EPR spectra in frozen (120 K) dichloromethane-toluene (1:1) solution. Electronic spectra of the complexes display several absorptions within 470–270 nm due to ligand-to-metal charge transfer and ligand centred transitions. The complexes are redox active and display a Ru(III) → Ru(II) reduction and a Ru(III) → Ru(IV) oxidation in the potential ranges ?0.66 to ?0.70 V and 0.75 to 0.80 V (vs. Ag/AgCl), respectively.     

Versatility in the binding of 2-pyrazinecarboxylate with iron. Synthesis, structure and magnetic properties of iron(II) and iron(III) complexes

The synthesis and characterization of two new iron(II) complexes, [Fe(pca)2(py)2].py (1) and {[Fe(pca)2(H2O)].H2O}n (2) and one new iron(III) complex, Na2{[Fe(pca)()]2O}.2H2O.2CH3CN (3) (pca- stands for 2-pyrazinecarboxylate), are reported. Complex 1 is obtained from the reaction of iron powder with 2-pyrazinecarboxylic acid. The reaction of Fe(ClO4)3.10H2O with Hpca in the presence of 3 equiv. of Bu4NOH yields 2, whereas the presence of NaOH yields 3. The molecular structure of 1 contains an iron(II) ion with a pseudo-octahedral environment resulting from the coordination of two pca- ligands in a bidentate chelating fashion and two pyridine molecules; pi-pi stacking interactions between pyridine and pyrazine rings lead to a one-dimensional chain. Complex 2 is an iron(II) coordination polymer with an infinite zig-zag motif and an Fe...Fe separation of 7.1 A. In 2, the pi-pi stacking interactions involving the pyrazine rings and the strong hydrogen bonds between the coordinated water molecule and the carboxylate oxygens of two pca- ligands result in a three-dimensional network structure. Complex 3 consists of an anionic micro-oxo-bridged diiron(III) core with two crystallographically distinct iron(iii) ions; the negative charge is compensated by two sodium cations. Complex 3 is assembled in a three dimensional network structure through coordination of Na(I) and hydrogen bond interactions. Temperature dependent magnetic susceptibility and M?ssbauer spectroscopic studies indicate that 1 and 2 have similar magnetic properties. Both complexes are paramagnetic above 12 K, whereas antiferromagnetic ordering is observed below 12 K. The magnetic properties of reveal strong intramolecular antiferromagnetic interactions between the two iron(III) ions with a J value of -221 cm(-1); no long range intermolecular magnetic coupling is observed between 295 and 4.2 K.     

Amine adducts and piperidinido compounds of iron(III)

Summary Piperidine reacts with the FeCI(o-H₂NC₆H₄CO₂)₂ · H2O, (1) and FeCl(o-HOC₆H₄CO₂)₂ · H2O, (2), to give the piperidinido-N complexes, Fe(NC₅H₁₀)(o-H₂NC₆H₄CO₂)₂ and Fe(NC₅H₁₀)(o-OC₆H₄CO₂), respectively. n-Butylamine and pyridine, combine with (1) and (2) either by removal of water or by formation of simple addition compounds or chelate rings. The i.r. spectra, molar conductances, magnetic moments, molecular weights and thermal decompositions of some of these products have been studied.     

Mixed ugand complexes of iron(III) derived from its dithiocarbamato complexes

Three different types of iron(III) complexes, Fe(A)₃, Fe(A)₂(A') and Fe(A)(A')₂, whereA is either piperidyldithiocarbamate or morpholyl dithiocarbamate andA' is glycine(oxine) acetylacetone have been prepared by reacting Fe(III) salt with sodium salt of piperidinedithiocarbamic acid or morpholine-dithiocarbamic acid and acetylacetone(oxine)-glycine in different ratios. The mixed ligand complexes have been characterised by elemental analysis, magnetic susceptibility measurements, infrared, electronic spectral techniques and by thermal analysis. Electronic spectral studies suggests that all the complexes possess distorted octahedral geometry. The magnetic moment of the high spin iron(III) complexes lies in the range of 5.88–6.00 and for low spin lies in the range of 3.36–4.34 B.M. TG studies show one step decomposition of complexes and formation of Fe₂O₃ at the end of the step.