An anomalous spin-polarization mechanism in high-spin manganese(III) porphyrin complexes

Confluence of NMR for paramagnetic molecules and the complementary density functional theory calculations reveals an anomalous spin-polarization mechanism that is maximized in high-spin d(4) complexes. It is critical to realize this mechanism to correctly rationalize the spin-density distribution around the porphyrin macrocycle.     

High-frequency and -field EPR investigation of a manganese(III) N-confused porphyrin complex, [Mn(NCTPP)(py)2

We report the first high-frequency and -field electron paramagnetic resonance (HFEPR) study of a Mn(III) N-confused porphyrin (NCP) complex (NCP is also known as inverted porphyrin or 2-aza-21-carbaporphyrin). We have found a striking variation in the electronic properties of the S = 2 Mn(III) ion coordinated by NCP compared to other Mn(III) porphyrinoid complexes. Thus, inversion of a single pyrrole ring greatly changes the equatorial ligand field exerted and leads to large magnitudes of both the axial and rhombic zero-field splitting [respectively, D = -3.084(3) cm(-1), E = -0.608(3) cm(-1)], which are unprecedented in other Mn(III) porphyrinoids.     

Definitive spectroscopic determination of zero-field splitting in high-spin cobalt(II)

A high-spin Co(II) complex (3d(7), S = 3/2), Co(PPh(3))(2)Cl(2) (Ph = phenyl), has been investigated in the solid state by both high-frequency and -field electron paramagnetic resonance (HFEPR) and by variable-temperature, variable-field magnetic circular dichroism (VTVH-MCD). In HFEPR spectroscopy, the combination of variable sub-THz frequencies generated by backward wave oscillators (150-700 GHz, corresponding to energy 5-23 cm(-1)) and high magnetic fields (0-25 T) constitutes a novel experimental technique allowing accurate determination of a complete set of spin Hamiltonian parameters for this complex: D = -14.76(2) cm(-1), E = 1.141(8) cm(-1), g(x) = 2.166(4), g(y) = 2.170(4), g(z) = 2.240(5). Independent VTVH-MCD studies on multiple absorption bands of the complex yield D = -14(3) cm(-1), E = 0.96(20) cm(-1) (absolute value of E/D = 0.08(2)), g(x) = 2.15(5), g(y) = 2.16(4), and g(z) = 2.17(3). This very good agreement between HFEPR and MCD indicates that there is no inherent discrepancy between these two quite different experimental techniques. Thus, depending on the nature of the sample, either can be reliably used to determine zero-field splitting parameters in high-spin Co(II), with the HFEPR being more accurate but VTVH-MCD being more sensitive.     

Computation of hyperfine tensors for dinuclear Mn(III) Mn(IV) complexes by broken-symmetry approaches: anisotropy transfer induced by local zero-field splitting

Based on broken-symmetry density functional calculations, the (55)Mn hyperfine tensors of a series of exchange-coupled, mixed-valence, dinuclear Mn(III) Mn(IV) complexes have been computed. We go beyond previous quantum chemical work by fully including the effects of local zero-field splitting (ZFS) interactions in the spin projection, following the first-order perturbation formalism of Sage et al. [J. Am. Chem. Soc. 1989, 111, 7239]. This allows the ZFS-induced transfer of hyperfine anisotropy from the Mn(III) site to the Mn(IV) site to be described with full consideration of the orientations of local hyperfine and ZFS tensors. After scaling to correct for systematic deficiencies in the quantum chemically computed local ZFS tensors, good agreement with experimental (55)Mn anisotropies at the Mn(IV) site is obtained. The hyperfine coupling anisotropies on the Mn(III) site depend sensitively on structural distortions for a d(4) ion. The latter are neither fully reproduced by using a DFT-optimized coordination environment nor by using experimental structures. For very small exchange-coupling constants, the perturbation treatment breaks down and a dramatic sensitivity to the scaling of the local ZFS tensors is observed. These results are discussed with respect to ongoing work to elucidate the structure of the oxygen-evolving complex of photosystem II by analysis of the EPR spectra.     

Redox chemistry of mononuclear manganese(II), binuclear manganese(III) and binuclear mixed manganese(II)-manganese(III) complexes with 3-aminopyrazine-2-carboxylate in dimethylsulphoxide

Summary Mn^II forms a yellow mononuclear species with the title ligand having a 12 stoichiometry and whose conditional stability constant is 8.9 × 10¹⁰ m ^–2. The c.v. of this complex shows an oxidation at +0.78V versus s.c.e. Controlled-potential electrolysis at +0.80V versus s.c.e. yields a binuclear species of Mn^III with a 12 metal:ligand stoichiometry.The addition of Mn^III(urea)₆(ClO₄)₃ to a solution of the ligand produces a mononuclear complex of Mn^III if the concentration of the metal ion is less than 1 mM. At higher concentrations a binuclear species is obtained. The latter is reduced in two steps, at +0.24 and –0.58 V versus s.c.e. Controlled-potential electrolysis at 0.0 V produces a dark green complex after the transfer of 0.5 equivalents of charge per mole of Mn. This binuclear L₂Mn^II-Mn^IIIL₂ mixed-valence complex can be obtained only by electrolysis of the binuclear L₂Mn^IIIMn^IIIL₂ species. Attempts to prepare the complex chemically were unsuccessful - the binuclear Mn^III species was obtained in every case.Author to whom all correspondence should be directed.     

High-frequency and -field electron paramagnetic resonance of high-spin manganese(III) in tetrapyrrole complexes

High-field and -frequency electron paramagnetic resonance (HFEPR) spectroscopy has been used to study three complexes of high spin Manganese(III), 3d4, S = 2. The complexes studied were tetraphenylporphyrinatomanganese(III) chloride (MnTPPCI), phthalocyanatomanganese(III) chloride (MnPcCl), and (8,12-diethyl-2,3,7,13,17,18-hexamethylcorrolato)manganese(III) (MnCor). We demonstrate the ability to obtain both field-oriented (single-crystal like) spectra and true powder pattern HFEPR spectra of solid samples. The latter are obtained by immobilizing the powder, either in an n-eicosane mull or KBr pellet. We can also obtain frozen solution HFEPR spectra with good signal-to-noise, and yielding the expected true powder pattern. Frozen solution spectra are described for MnTPPCl in 2:3 (v/v) toluene/CH2Cl2 solution and for MnCor in neat pyridine (py) solution. All of the HFEPR spectra have been fully analyzed using spectral simulation software and a complete set of spin Hamiltonian parameters has been determined for each complex in each medium. Both porphyrinic complexes (MnTPPCl and MnPcCl) are rigorously axial systems, with similar axial zero-field splitting (zfs): D approximately -2.3 cm(-1), and g values quite close to 2.00. In contrast, the corrole complex, MnCor, exhibits slightly larger magnitude, rhombic zfs: D approximtely -2.6 cm(-1), absolute value(E) approximately 0.015 cm(-1), also with g values quite close to 2.00. These results are discussed in terms of the molecular structures of these complexes and their electronic structure. We propose that there is a significant mixing of the triplet (S = 1) excited state with the quintet (S= 2) ground state in Mn(III) complexes with porphyrinic ligands, which is even more pronounced for corroles.     

Structural and physical characterization of tetranuclear [Mn(II)3Mn(IV)] and [Mn(II)2Mn(III)2] valence-isomer manganese complexes

Two tetranuclear Mn complexes with an average Mn oxidation state of +2.5 have been prepared. These valence isomers have been characterized by a combination of X-ray crystallography, X-ray absorption spectroscopy, and magnetic susceptibility. The Mn(II)3Mn(IV) tetramer has the Mn ions arranged in a distorted tetrahedron, with an S = 6 ground spin state, dominated by ferromagnetic exchange among the manganese ions. The Mn(II)2Mn(III)2 tetramer also has a distorted tetrahedral arrangement of Mn ions but shows magnetic behavior, suggesting that it is a single-molecule magnet. The X-ray absorption near-edge structure (XANES) spectra for the two complexes are similar, suggesting that, while Mn XANES has sufficient sensitivity to distinguish between trinuclear valence isomers (Alexiou et al. Inorg. Chem. 2003, 42, 2185), similar distinctions are difficult for tetranuclear complexes such as that found in the photosynthetic oxygen-evolving complex.     

Catalytic studies of 2-benzthiazolethiol (BzTa)-linked manganese(III) and cobalt(II) porphyrin complexes

Four 2-benzthiazolethiol (BzTa)-linked porphyrins (1)–(4), and their complexes with Co^II and Mn^III, (5)–(12), were prepared and characterized by elemental analysis, ¹H-n.m.r., i.r., u.v.–vis. and mass spectra. The hydroxylation of cyclohexane in the presence of these complexes and PhIO under mild conditions was investigated. The catalytic activities of these complexes were higher than that of corresponding TPPMn^IIICl and TPPCo^II species respectively, which indicated that the terminal group, BzTa, played an important role in the catalysis. A possible mechanism is proposed.     

Electrochemical reduction of Fe(III), Cr(III), and Mn(III) porphyrin complexes in DMSO

The half-wave potentials are given for the electrochemical reduction of Fe(III), Cr(III), and Mn(III) porphyrin complexes. Cyclic voltamperometry was used to study the reversibility of these reactions. An effect was demonstrated for the structure of the porphyrin ligand on the half-wave potentials for the reduction of the Mn(III) complexes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1665–1668, July, 1991.     

Studies on binuclear hydroxo/carboxylato-bridged manganese(III) complexes and a mononuclear manganese(III) complex involving salen type ligands

Synthesis of six hydroxo-bridged binuclear manganese(III) complexes of formulae [MnL-X-MnL](ClO₄) [X = OH (1–6)] along with a mononuclear manganese(III) complex (7) [Mn(L)(L′)(MeOH)₂] [HL′ = 2-(2-hydroxy-phen-yl)benzimidazole] and two carboxylate-bridged binuclear manganese(III) complexes (8) and (9) are described. The complexes have been characterized by the combination of i.r., u.v.-vis spectroscopy, magnetic moments and by their redox properties. The electronic spectra of all the complexes exhibit almost identical features consisting of two d–d bands at ca. 550 and 600 nm, one MLCT band at ca.400 nm, together with two π–π^* intra-ligand transitions at ca. 250 nm and ca.300 nm. Room temperature magnetic data range from μ = 2.7–3.0 BM indicates some super-exchange between the binuclear metal centers via bridging hydroxo/carboxylato groups. The X-ray crystal structure of the binuclear complex (5) revealed that it has a symmetric Mn^IIIN₂O₂ core bridged by a hydroxyl group. The X-ray analysis of the mononuclear complex (7) showed that the manganese-center possesses a distorted octahedral geometry. Electrochemical properties of hydroxo-bridged manganese(III) complexes (1–6) show identical features consisting of an irreversible and a quasi-reversible reduction corresponding to the Mn₂^III → Mn^IIMn^III → Mn^IIMn^II couples in the voltammogram. It was found that electron withdrawing substituents on the ligand result in easier reduction. Complex (7) displays an irreversible reduction at 0.08 V and a reversible oxidation at 0.45V assignable to the Mn^III → Mn^II reduction and Mn^III → Mn^IV oxidation, respectively. The carboxylate-bridged compound (8) exhibits two irreversible oxidations at 0.4 and 0.6 V, probably due to Mn₂^III → Mn^IIIMn^IV → Mn^IVMn^IV oxidations and shows a quasi-reversible reductive wave at −0.85 V, tentatively assigned to Mn₂^III → Mn^IIMn^III reduction.     

Magnetic properties of diruthenium(II,III) carboxylate compounds with large zero-field splitting and strong antiferromagnetic coupling

The magnetic properties of mixed-valent compounds of general formula Ru2Cl(mu-O2CR)4 [R = CH2-CH3 (1), C(Me)=CHEt) (2)] have been studied in the 2-300 K temperature range. This magnetic study also includes a revision of the magnetic properties of the complex Ru2Cl(mu-O2CCMePh2)4 (3). Compounds 1-3 show a linear structure and a strong antiferromagnetic coupling between the diruthenium units through the chlorine atoms according to previous studies. Two fitting models to explain the magnetic properties of these complexes that incorporate a large zero-field splitting together with a strong antiferromagnetic coupling are described. These models consider that each diruthenium unit (S = 3/2) is magnetically coupled to the nearest diruthenium unit and ignores the longer distance magnetic coupling. The fitting models were found to be successful in fitting the magnetic data of the linear diruthenium(II,III) complexes. The zero-field splitting, D, and the antiferromagnetic coupling, zJ, vary from 37.8 to 48.0 cm-1 and from -7.43 to -13.30 cm-1, respectively, for complexes. The D values are similar to those calculated for the nonlinear diruthenium(II,III) compounds and confirm the validity of the proposed fitting models.     

Oxidation of aromatic monoterpenes with hydrogen peroxide catalysed by Mn(III) porphyrin complexes

The oxidation of carvacrol 1, thymol 2 and p-cymene 3 with hydrogen peroxide catalysed by Mn(III) porphyrins is reported. The oxidation of 1 and 2 selectively originates thymoquinone 6. From the oxidation of p-cymene 3, the isolated major products 7–10, were formed from the oxidation of positions 7 and 8 of the substrate, although minor amounts of thymoquinone 6 were also formed. The efficiency and selectivity of the catalytic systems and the structural characterisation of the products obtained will be discussed.     

Copper(II) complexes of inverted porphyrin and its methylated derivatives

The inverted porphyrins 2-aza-5,10,15,20-tetraphenyl-21-carbaporphyrin (CTPPH2) and its methylated derivatives 2-aza-2-methyl-5,10,15,20-tetraphenyl-21-carbaporphyrin (2-NCH3CTPPH) and 2-aza-2-methyl-5,10,15,20-tetraphenyl-21-methyl-21-carbaporphyrin (2-NCH3-21-CH3CTPPH) stabilize the rare organocopper(II) complexes (CTPP)CuII (1), (2-NCH3CTPP)CuII (2), (CTPPH)CuIIX (3-X), (2-NCH3CTPPH)CuIIX (4-X) (X = Cl-, TFA), and (2-NCH3-21-CH3CTPP)CuIICl (5). The EPR spectra recorded for 1, 2, 4, and 5 revealed typical features diagnostic of the copper(II) electronic structure. The superhyperfine coupling pattern indicates a presence of three nitrogen donors in the first coordination sphere. An addition of HX acid to 1 and 2 to yield the species 3-X and 4-X. The reaction mechanism includes protonation of the inner C(21) carbon accompanied by an axial coordination of anion. Methylation of (2-NCH3CTPP)CuII (2) with methyl iodide resulted in formation of (2-NCH3-21-CH3CTPP)CuIICl (5) which implies an existence of a sigma-carbanion-copper(II) bond in 2. The 2H NMR investigations carried out for the pyrrole deuterated derivatives (CTPP-d7)CuII, (2-NCH3-21-CH3CTTP-d7)CuIICl, and the methyl deuterated (2-NCH3-21-CD3CTPP)CuIICl one confirmed independently the copper(II) electronic structure with the considerable dx2-y2 metal orbital contribution to the SOMO. The redox properties of copper(II) inverted porphyrins were studied by the cyclic and differential pulse voltammetry. The halfwave potentials indicate a metal-centered oxidation of 1 (390 mV) and 2 (343 mV). The dimethylated homologue 5 reveals the reduction process at -224 mV attributed to the CuII/CuI transformation.     

Polynuclear manganese complexes with the dicarboxylate ligand m-phenylenedipropionate: a hexanuclear mixed-valence (3Mn(III), 3Mn(IV)) complex

The dicarboxylate group m-phenylenedipropionate (mpdp(2)(-)) has been used for the synthesis of four new Mn compounds of different nuclearities and oxidation states: [Mn(2)O(mpdp)(bpy)(2)(H(2)O)(MeCN)](ClO(4))(2) (3), [Mn(3)O(mpdp)(3)(py)(3)](ClO(4)) (4), [Mn(3)O(mpdp)(3)(py)(3)] (5), and [Mn(6)O(7)(mpdp)(3)(bpy)(3)](ClO(4)) (6). Compound 3 (2Mn(III)) contains a [Mn(2)(micro-O)](4+) core, whereas 5 (Mn(II), 2Mn(III)) and 4 (3Mn(III)) contain the [Mn(3)(micro(3)-O)](6+,7+) core, respectively. In all three compounds, the mpdp(2)(-) ligand is flexible enough to adopt the sites occupied by two monocarboxylates in structurally related compounds, without noticeable distortion of the cores. Variable-temperature magnetic susceptibility studies establish that 3 and 5 have ground-state spin values of S = 0 and S = 1/2, respectively. Compound 6 is a highly unusual 3Mn(III), 3Mn(IV) trapped-valent compound, and it is also a new structural type, with six Mn atoms disposed in a distorted trigonal antiprismatic topology. Its electronic structure has been explored by variable-temperature measurements of its dc magnetic susceptibility, magnetization vs field response, and EPR spectrum. The magnetic data indicate that it possesses an S = 3/2 ground state with an axial zero-field splitting parameter of D = -0.79 cm(-)(1), and this conclusion is supported by the EPR data. The combined results demonstrate the ligating flexibility of the mpdp(2)(-) ligand and its usefulness in the synthesis of a variety of Mn(x) species.     

A spectral and electrochemical study of mononuclear manganese(III) complexes of a polybenzimidazolyl ligand

Summary A series of Mn^III complexes with stoichiometry [MnLX](Y)₂ have been synthesized utilizing an exogenous anionic ligand, X^- = OAc, SCN or N₃, and the hexadentate ligand N,N,N,N-tetrakis[2(benzimidazolyl) methyl-1,2-ethanediamine] and its N-octyl derivative. The vis. spectra of the compounds are in keeping with a pseudo-C _4v , symmetry for the Mn^III ion, implying that all the pendant arms of the hexadentate ligand do not bind to the Mn^III centre. Cyclic voltammetric studies reveal that the E _1/2 for the Mn^III/Mn^IV couple shifts to positive values with SCN^- as the anionic ligand, implying that this anion stabilizes the Mn^III oxidation state, whereas E _1/2 data for N₃ ^- reveals that the anion destabilizes the Mn^III state.