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ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
The crystal and molecular structure of a series of oxo-molybdenun di-n-propyldithiocarbamates have been studied by X-ray diffraction methods. The compounds studied were di(oxo-di-n-propyldithiocarbamato) molybdenum VI (A), μ-oxo-bis-(di(oxo-di-n-propyldithiocarbamato) molybdenum V) (B), and oxo-bis-di-n-propyldithiocarbamato molybdenum IV (C). Comp...
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
The electronic ground state of the ferricytochromes c' has been and continues to be the subject of debate, and evidence for a quantum mechanically admixed S=3/2,5/2 ground state in these molecules has often been challenged. This review covers work on model heme complexes in which the properties of the S=3/2,5/2 spin-state admixture have been establ...
The catalytic cycle intermediates of heme peroxidases, known as compounds I and II, have been of long standing interest as models for intermediates of heme proteins, such as the terminal oxidases and cytochrome P450 enzymes, and for non-heme iron enzymes as well. Reports of resonance Raman signals for compound I intermediates of the oxo-iron(IV) po...
Two dioxygen adducts of thiolato-iron(II) porphyrins, [K(⊂ 222)][Fe(TPpivP)(SC6HF4)(O2)] 1a and [Na(⊂ 18c.6)][Fe(TPpivP)(SC6HF4)(O2)] 2 were synthesized by reaction of O2 with five-coordinate, high-spin, cryptated alkali metal thiolato-iron(II) ‘picket fence’ porphyrinate. They were characterized by visible and infrared spectroscopy: λmax (log ɛ) =...
For Abstract see ChemInform Abstract in Full Text.
For Abstract see ChemInform Abstract in Full Text.
The phenyliron derivative, [Fe(oetpp)C6H5)]SbCl6 (2) generated in dichloromethane by oxidation of the phenyliron(III) complex, Fe(III) (oetpp)C6H5 (1) of the 2,3,7,8,12,13,17,18-octaethyl- 5,10,15,20-tetraphenylporphyrin with 1 equiv. of phenoxathiinylium hexachloroantimonate, [C12H8OS]SbCl6, was studied by Mossbauer spectroscopy. This compound exh...
It is generally assumed that the putative compound I (cpd I) in cytochrome P450 should contain the same electron and spin distribution as is observed for cpd I of peroxidases and catalases and many synthetic cpd I analogues. In these systems one oxidation equivalent resides on the Fe(IV)=O unit (d(4), S=1) and one is located on the porphyrin (S'=1/...
The chloroiron(III) complex Fe(dpp)Cl (1) of the peripherally crowded 2,3,7,8,12,13,17,18-octaphenyl-5,10,15,20-tetraphenylporphyrin or dodecaphenylporphyrin (dpp), has been synthesized and characterized by X-ray crystallography, normal-coordinate structural decomposition analysis (NSD), EPR and Mössbauer spectroscopy and magnetic susceptibility me...
The chloroiron(III) complexes of the partially peripherally crowded 2,3-diethyl-2,3,12,13-tetraethyl-, 2,3,7,8-
tetraethyl-, and 2,3,7,8,12,13-hexaethyl-5,10,15,20-tetraphenylporphyrins have been synthesised and their X-ray structures have been determined. The porphyrins present in these molecules are non-planar and assume asymmetric predominately...
Samples of the dithionite-reduced FeFe protein (the dinitrogenase component of the Fe-only nitrogenase) from Rhodobacter
capsulatus have been investigated by 57Fe Mössbauer spectroscopy and by Fe and Zn EXAFS as well as XANES spectroscopy. The analyses were performed on the basis of data known for the FeMo cofactor and the P cluster of Mo nitrogena...
The synthesis, spectroscopic properties, and electrochemistry of six different alkyl- and aryl-substituted Co(III) corroles are presented. The investigated compounds contain methyl, ethyl, phenyl, or substituted phenyl groups at the eight β-positions of the corrole macrocycle and four derivatives also contain a phenyl group at the 10-meso position...
The synthesis, spectroscopic properties, and electrochemistry of (BCA)Co(2) and (BCB)Co(2) are described where BCA and BCB represent biscorroles linked by an anthracenyl (A) or a biphenylenyl (B) bridge. The pyridine and CO binding properties of (BCA)Co(2) and (BCB)Co(2) are also presented, and one of the compounds in its pyridine-ligated form, (BC...
Oxoferryl porphyrin π-cation radical active sites of compound I intermediates which are found in enzymes such as peroxidases and catalases have been extensively modeled by oxidized synthetic metalloporphyrins. The electronic symmetry states of these compounds were initially assigned on the basis of electronic absorption data. In recent years new ex...
Iron and manganese hemes are "high-valent" when the valence state of the metal exceeds III. Redox chemistry of the high valent metal complexes involves redistribution of holes and electrons over the metal ion and the porphyrin and axial ligands, defined as valence tautomerism. Thus, catalytic pathways of heme-containing biomolecules such as peroxid...
New nickel(ii) bisoxocorrole complexes have been synthesized and characterized. Two nickel bisoxocorrole isomer complexes are formed in a 1:1 ratio when a biscorrole, where an anthracenyl bridge links the two macrocycles in a face to face arrangement, is metallated by nickel in air. Evidence for the insertion of an oxo group at one of the meso posi...
Freeze-quenched intermediates of substrate-free cytochrome 57Fe-P450(cam) in reaction with peroxy acetic acid as oxidizing agent have been characterized by EPR and Mossbauer spectroscopy. After 8 ms of reaction time the reaction mixture consists of approximately 90% of ferric low-spin iron with g-factors and hyperfine parameters of the starting mat...
The term ‘high-valent’ refers to iron complexes of porphyrins and related macrocycles in which the oxidation state of the iron center exceeds III. High-valent iron porphyrins and chlorins are important biological transients whose intermediacy has been demonstrated in numerous peroxidase and catalase enzymes. Two species, compounds I and II, are spe...
The generation of six-coordinate oxoiron (IV) tetramesitylporphyrin pi-caption radical complexes by m-CPBA (meta-chloroperbenzoic acid) oxidation of ferric tetramesitylporphyrin derivatives in butyronitrile at - 78 degrees C was investigated. UV-Vis and EPR spectroscopies indicate that the axial ligand present in the ferric starting derivatives is...
To examine the porphyrin-core expansion and the conformational variations induced by a change in the coordination sphere of nickel(II) from four-coordinate, low-spin (S = 0) to six-coordinate, high-spin (S = 1), several nickel(II) derivatives of tetraphenylporphyrins, substituted in their beta-pyrrole positions with electron-withdrawing groups, wer...
Despite similar ring deformations in solution and in the solid state, the chloroiron(III) derivative of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin ([FeCl(oetpp)], shown schematically) prepared in this study exhibits only a very weak quantum-mechanical admixture of spin S=3/2 (only 4-10 %) with spin S=5/2. In contrast, for the var...
Trotz ähnlicher Ringdeformationen in Lösung und im Festkörper weist das synthetische Chloroeisen(III)-Derivat von 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetraphenylporphyrin (oetpp), [FeCl(oetpp)] (hier schematisch dargestellt), nur eine sehr schwache quantenmechanische Beimischung eines S=3/2-Spinzustands (nur 4–10 %) zum S=5/2-Spinzustand auf....
The hydroxylation of aniline with H2O2 as the oxidant has been utilized to probe the catalytic activity of the water-insoluble model porphyrin in a water-soluble MCM-41 system and to investigate the catalytic activity and operational stability of microperoxidase-8 upon its incorporation into MCM-41. Our results demonstrate that metalloporphyrins su...
This study describes the catalytic properties of manganese microperoxidase 8 [Mn(III)MP8] compared to iron microperoxidase 8 [Fe(III)MP8]. The mini-enzymes were tested for pH-dependent activity and operational stability in peroxidase-type conversions, using 2-methoxyphenol and 3,3'-dimethoxybenzidine, and in a cytochrome P450-like oxygen transfer r...
The molecular structure of the methoxy-iron(III) derivative |(Me,OH)-Fe(OMe)| of the strapped porphyrin (5,15-(o,o′(2-methyl-2′-hydroxy-3,3′-diamidobiphenyl)-diphenyl)-porphyrin (1(Me,OH)) is reported. The 2-methyl-2′-hydroxy-substituted biphenyl unit and the porphyrin ring are covalently bound together by two amido-groups linking the 3,3′-position...
The vanadyl complex oxo[5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato-kappa(4)N] vanadium(Iv) dichloromethane solvate, [VO(C44H8F20N4)]. CH2Cl2, crystallizes in the monoclinic space group P2(1)/c, with four molecules per unit cell. The V atom is found to lie 0.5237(5)Angstrom above the mean plane of the porphyrin core. The average V-N distance...
The mechanism of spin‐lattice relaxation has been investigated in the “picket‐fence” porphyrin [Fe(CH3COO)(TPpivP)]-, a high‐spin iron(II) complex with unusual large quadrupole splitting of 4.25 mm s-1, by conventional Mssbauer spectroscopy as well as by nuclear resonant forward scattering (NFS). Superparamagnetism with
a blocking temperature of ab...
Nuclear resonant forward scattering (NFS) of synchrotron radiation was employed as Mössbauer spectroscopy in the time domain only recently, while conventional Mössbauer spectroscopy in the energy domain is widely applied since its discovery in 1958. Experimental setup and theoretical background required for NFS are explained, and examples are given...
The synthesis of a series of meso-5,15-diphenylporphyrins strapped by 2,2'-disubstituted biphenyl units (6H(2), 7H(2), 8H(2)) is described. The biphenyl straps used are linked via their 3,3'-positions by CH(2)O groups to ortho-positions of the phenyl rings of the 5,15-diphenylporphyrins. The straps of these porphyrins have their 2,2'-positions occu...
Nuclear resonant forward scattering (NFS) of synchrotron radiation represents Mossbauer spectroscopy in the time domain. This new technique complements the conventional nuclear resonance absorption, e.g. Mössbauer spectroscopy in the energy domain, by supplying highly brilliant, polarized, collimated and timed radiation. In NFS the hyperfine intera...
Synthesis of new symmetrical cylindrical macrotricyclic ligands 1a,b, where two cyclam subunits are linked through nitrogen atoms by two aromatic chains of various lengths (meta-xylylenyl, para-xylylenyl) has been achieved. These compounds have been prepared according a five step procedure. The readily available trisheteroprotected cyclam 4 has bee...
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and...
The macrocycles 2-oxa-3-oxotetramesityl- and 2-oxa-3-oxotetrakis(2,6-dichlorophenyl)porphine (porpholactones) and their iron complexes have been synthesized and characterized. The crystal structure of the chloroferric complex of the 2,6-dichlorophenyl-substituted porpholactone shows that iron is in an environment of effective 4-fold symmetry despit...
The chloro-iron(III) complex of the tetraphenylporphyrin tetrabrominated at the antipodal β-pyrrole positions [(7,8,17,18-tetrabromo-5,10,15,20-tetraphenyl)porphyrin]
has been synthesized and characterized by spectroscopy and X-ray crystallography. The iron atom is bonded to the chloride
ion and the four pyrrole nitrogens. The Fe-Cl bond distance...
Two novel bis(lutetium) cofacial anthracene- or biphenylene-bridged bis(porphyrins), (DPA)[Lu(OH)]2·CH3OH and (DPB)[Lu(OH)]2·CH3OH, have been prepared and characterized by UV−vis, 1H NMR, IR, and mass spectrometry. The structure of the two bis(lutetium) porphyrins has been resolved by a X-ray diffraction study. The two lutetium atoms are bridged by...
The title compound, [Ni(C48H24N8)(C5H5N)(2)].2CH(4)O, is a high-spin bis(pyridine)-Ni-II derivative of an antipodally beta-pyrrole-tetracyano-substituted meso-tetraphenylporphyrin. The [Ni(py)2{tpp(CN)(4)}] molecule [py is pyridine and tpp(CN)(4) is 7,8,17,18-tetracyano-5,10,15,20-tetraphenylporphyrinato] lies on a crystallographic centre of symmet...
The [Cu-2(terpy)(2)(CN)](3+) cation (terpy is 2,2':6',2 ''-terryridine) is non-centrosymmetric and contains two Cu-II centres bridged by a disordered cyano group. The overall geometry around both metallic centres can be described as a distorted octahedron. The equatorial coordination plane is occupied by the N atoms of the tridentate terpy ligand a...
The objective of this study it to characterize high-valent speno gpnrr.ited from peroxy acid oxidation of ferric picket fence porphyrins. ba.sed on the picket fence complexes first reported by Colhnan et at. in 1970. If model the influence of active site aminu acid residues on the high valent intermediate. To simplify characterization of the high-v...
The molecular structure of the chloroiron(III) porphyrinate [FeIIICl- (tmtmp)] (1) is described. The doming off the bifacially encumbered tmtmp dianionic ligand present in 1 is characterized by a separation of 0.09 (1) Å between the mean plane of the four pyrrole nitrogens (4NP) and that of the porphyrin core. The coordination polyhedron of the fiv...
A comparison of the exchange interactions arising in the peroxidase and catalase Compound I intermediates and their iron(IV)-oxo
porphyrin π-cation radical models, both of which are two oxidizing equivalents above the ferric state, suggests that in the
models the oxidizing equivalent is localized on the porphyrin ring, while in the proteins it is...
Either a metal atom or the phthalocyanine ligand is the site of the first oxidation of the heteronuclear triple-decker complexes of type 1, depending on whether they contain an oxidizable CeIII ion or not. Now the first X-ray structure of such a heteronuclear triple-decker complex (1, M Ce, M′ Gd, p oep) has also been achieved.
An einem Metallatom oder am Phthalocyanin(pc)- Liganden findet die erste Oxidation der heteronuclearen Tripeldeckerkomplexe vom Typ 1 statt, je nachdem ob sie ein oxidierbares CeIII-Ion enthalten oder nicht. Mit 1, M = Ce, M' = Gd, p = oep, gibt es nun auch den ersten röntgenographisch charakterisierten derartigen heteronuclearen Tripeldecker- komp...
A series of (oxoferryl)porphyrin pi-cation radicals generated from porphyrins substituted at the meso positions with highly electron-withdrawing aryl groups has been characterized: tetrakis-5,10,15,20-(2,6-dichlorophenyl)-, 5-(2-chloro-6-nitrophenyl)-10,15,20-tris(2,6-dichlorophenyl)-, and 5-(2,6-dinitrophenyl)-10,15,20-tris(2,6-dichlorophenyl)porp...
The X-ray crystal structure determination of the title copper derivative, [bis(6-methyl-2-pyridylmethyl) sulfide-N,N', S] bis(trifluoromethylsulfonato-O)copper (II) dichloromethane solvate, shows that this compound contains monomeric [Cu(DMPT)OSO2CF3)(2)] molecules in which the Cu-II ion in surrounded by a tridentate DMPT ligand [Cu-N1 2.001(4), Cu...
In the present study the in vitro and in vivo aromatic ring hydroxylation of a series of amino and/or methyl containing fluorobenzenes, i.e. 3-fluoro(methyl)anilines, was investigated and compared to the calculated density distribution of the reactive frontier pi-electrons of the aromatic substrate. This was done (1) to study to what extent the reg...
Four novel metal-free, potentially heterodinucleating ligands, P1, P2, P3, and P4, have been successfully synthesized and characterized. These ligands consist of a 5,15-diphenylporphyrin with a covalently appended strap containing potentially tridentate groups: 2,6-bis[(aminotosyl)methyl]pyridine (P1), 2,6-bis[(aminomethyl)methyl] pyridine (P2),2,6...
The synthesis and spectroscopic properties of the neutral metal(III) heteroleptic porphyrin-phthalocyanine double-decker sandwich-like complexes \(TPP)M(III)(Pc)\ (1) are reported (TPP and Pc = dianions of tetraphenylporphyrin and phthalocyanine, respectively; M = La, Pr, Nd, Eu, Gd, Er, Lu, and Y). The electron transfer reactions of these M(III) c...
Partial photodissociation of two carbonmonoxy-porphyrin complexes, a bridged and a fenced one, has been achieved. The results from monitoring the recombination point to an important influence of the solvent matrix on the recombination rates.
The MnIVO unit in the five-coordinate oxo(porphyrinato)manganese(IV) complex 2, which is formed by oxidation of the bromo(porphyrinato)manganese(III) complex 1 with potassium peroxycarbonate, was characterized by X-ray absorption spectroscopy. The relatively long MnO bond (1.69±0.03 A) is probably attributable to the high-spin state and the low pol...
In order to study structural influences on the interaction of Fe(IV) (S=1) and porphyrin cation radical (S=1/2) in high-valent iron porphyrin complexes of the type X-(TMP)Fe=O+(Cl–), X=I, Br2, Br4 were generated by mCPBA oxidation of corresponding Fe(III) porphyrins. The halogen substitution at the peripheral positions of the porphyrin leads to dis...
Encumbered heme models have been designed over the years to enforce the Fe-C-O unit to adopt a bent geometry as reported earlier in myoglobin and to examine the consequences upon the reactivity. This work deals with ''hybrid'' heme models in which a variable amount of distal steric hindrance is provided by a chain which is rigidly maintained in a c...
A systematic electrochemical, redox, optical absorption, and resonance Raman spectroscopic study of 22 gadolinium and cerium double- and triple-decker tetraphenylporphyrin-phthalocyanine (TPP-Pc) complexes is reported. The work is aimed at elucidating the extent of the localization or delocalization among the chromophore ligands in the mixed comple...
Despite four additional electron-withdrawing substituents, the octahalogenated porphyrins 2 are more easily oxidized than their tetra-halogenated counterparts 1. This apparent paradox can be explained by the structures of the molecules: porphyrins 2 are almost planar, whereas in 1 steric interactions are minimized by a saddle conformation, which ma...
Die octahalogenierten Verbindungen 2 sind stärker elektronenziehend substitutiert und dennoch leichter zu oxidieren als die tetrahalogenierten Derivate 1; dieser scheinbare Widerspruch läßt sich aufklären, wenn man die röntgenographisch ermittelten Strukturen beider Verbindungstypen vergleicht. Die Verbindungen 2 weichen ungünstigen Wechselwirkunge...
Subpicosecond time-resolved absorption studies have been carried out on a cerium porphyrin-phthalocyanine sandwich mixed dimer in the liquid and solid states. Following excitation, two relaxation processes having time constants of ≈ 1 and ≈ 40 ps are observed irrespective to the nature of the environment. The first process is attributed to the rela...
Despite significantly different molecular structures and redox potentials, the electronic properties of the oxoferryl cation radical of 1 (M FeIV O instead of M FeIIICl, obtained by oxidation of 1 with m-chloroperoxyben zoic acid), which shows saddle-shaped distortions as a result of its peripheral chloro substituents, are similar to those of the c...
Trotz unterschiedlicher Molekül Struktur und unterschiedlicher Redoxpotentiale ähneln sich die elektronischen Eigenschaften des Oxoferryl‐Radikalkations von 1 (M = Fe IV O anstelle von M = Fe III Cl, erhalten durch Oxidation von 1 mit m ‐Chlorperbenzoesäure), das auf‐grund seiner peripheren Chlorsubstituenten sattelförmig verzerrt ist, und die des...
Oxoferryl porphyrin pi cation radical species have been generated by the oxidative action of m-chloroperoxybenzoic acid on the triflato complexes of [tetrakis(2,6-dichlorophenyl)porphyrinato]- and [tetrakis(2,4,6-trimethoxyphenyl)porphyrinato]-iron(III) in methylene chloride/methanol-d4. The new high-valent complexes have been characterized by a va...
The ferrous and ferric form of a ("picket-fence" porphyrinato)(acetato)iron complex, [FeII/IIICH3CO2)(TPPivP)] -,0, were synthesized and characterized by UV-visible, 1H NMR, EPR, and Mössbauer spectroscopy. The structure of the ferrous complex was determined by X-ray diffraction. Crystal data at -100°C: [FeII(CH3CO2)(TPpivP)][NaC222]·C 6H5Cl (C90H1...
The X-ray structures of the beta-substituted-pyrrole tetraarylporphyrin 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetramesitylporphyrin (H2TMOBP), its nickel(II) complex (NiTMOBP), and the nickel(II) derivative of 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (NiTPFPOBP.1/2CH2Cl2) are reported. The synthesis of the fr...
The synthesis of α-(chlorofluoromethyl)-ornithine 7, -metatyrosine 8 and -glutamic acid 14 is described. Separation of diastereoisomers and relative configuration assignment by X-ray analysis are reported. Assignment of absolute configuration of the four enantiomers of α-(chlorofluoromethyl)-ornithine 7 is also described. The inhibitory properties...
Mössbauer investigations were performed in the ferrous and ferric form of the ‘picket-fence’ porphyrinato acetato iron complex
|Fe(CH3CO2) (TPpivP)|1−,0 at temperatures varying from 1.5–200K and in fields of 0–6.2T. The ferrous complex has an unusually large quadrupole splitting,
ΔEQ=+4.25mms−1. The quadrupole splitting in the ferric species, ΔEQ=+...
Oxoferrylporphyrin cation radical complexes were generated using the prophyrin dianions: tetrakis 2,6-dichlorophenyl (TDCPP)
and tetrakis 2,4,6-trimethoxyphenyl (TTMPP). Spin coupling between ferryl iron (S=1) and porphyrin radical S′=1/2), ligand
field interaction and hyperfine parameters of iron were studied by Mssbauer and EPR measurements and c...
The electrochemical oxidation of zirconium and hafnium double-deckers M(P)2 (M=Zr, Hf; P=OEP, TPP) (Scheme 1)2) leads to mono- and dications which show near infrared absorption bands which are of ≈ 2000 cm-1 higher energy than those of the corresponding cerium double-decker cations. [Zr(OEP)2]X, [Zr(OEP)2]X2, and [Zr(TPP)2]X (X=ClO4− and PF6−) are...
The yttrium diphthalocyanine [YPc2]·CH2Cl2 has been synthesized and its structure and magnetic properties are reported. They are compared to those of the nonsolvated derivative αYPc2, which is isostructural to NdPc2. In [YPc2]·CH2Cl2, the phthalocyanine macrocycles are packed above each other in order to form infinite chains parallel to the c axis...
The structure and magnetic properties of yttrium diphthalocyanine [YPc2].CH2Cl2 are reported. Phthalocyanine macrocycles are stacked above each other in one direction, with a staggered angle of 45°. One-dimensional organic ferromagnetism is emphasized for the first time, and discussed on the basis of an orbitally degenerate model. A comparison with...
The synthesis of new zirconium and hafnium bisporphyrinate double deckers M(P)2 (MZr, Hf; POEP, TPP)2,3) is described. The complexes are characterized by UV/Vis/NIR and 1H-NMR spectroscopy and cyclic voltammetry. As compared with MCe, the redox potentials or the energies of the nearinfrared absorption bands of the corresponding radical cations [M(P...
Thermische Stabilität, strukturelle Flexibilität und räumliche Nähe der Metallzentren: diese Eigenschaften sollen zweikernige Porphyrinkomplexe, die für viele Gebiete der Chemie von Interesse sind, haben. Nach diesen Anforderungen wurde der Porphyrinligand 1 entwickelt, der an einem flexiblen Spacer einen 1,4,8,11‐Tetraazacyclotetradecyl‐Rest trägt...
Thermal stability, structural flexibility, and spatial proximity of the metal centers—these properties are required of binuclear porphyrin complexes, which are of interest in many areas of chemistry. These criteria governed the design of a porphyrin ligand connected via a flexible spacer to a 1,4,8,11-tetraazacyclotetradecyl moiety. Its metalation...
Oxorhenium(V) porphyrins ReO(P)X (X = Cl, Br) or [ReO(P)]2O, or trichlororhenium(V) porphyrins ReCl3(P) (P = OEP, TPP, TTP, TAP, TCIP, TMP)2,3, respectively, are transformed into nitridorhenium(V) porphyrins ReN(P) with hydrazine hydrate in the presence of ethanol, in good yields. The diamagnetic complexes are stable towards hydrolysis and contain...
The iron(III) "picket-fence" porphyrin complex [FeIII(TPpivP)(OSO2CF3)(H 2O)] (1) was synthesized and characterized by its UV-visible, 1H NMR, EPR, magnetic, and Mössbauer properties. The X-ray structure of 1 was determined at -100°C. Crystal data: [Fe(TPpivP)(OSO2CF3)(H2O)] (C65H66N8O8F3SFe); monoclinic; a = 13.161 (3), b = 19.196 (6), c = 26.212...
The synthesis and characterization of the sodium 222 cryptated salts of the five-coordinate high-spin (2-methylimidazolato)iron(II) derivative 1 and the six-coordinate (imidazole)(imidazolato)iron(II) complex 2 of "picket-fence" porphyrin are reported. 1 crystallizes as the 2-methylimidazole bis(chlorobenzene) solvate, C102H121Ni4O10NaCl2Fe, in the...
Oxoferrylporphyrin cation radical complexes were generated by m-chloroperoxybenzoic acid oxidation of the chloro and trifluoromethanesulfonato complexes of tetramesitylporphyrinatoiron(III) [(TMP)Fe] and the trifluoromethanesulfonato complex of tetra(2,6-dichlorophenyl)porphyrinatoiron(III) [TPP(2,6-Cl)Fe]. Coupling between ferryl iron (S = 1) and...
The sym. bis(porphyrinates) (Ia)-(Ic) are obtained from the free base and Ce(III) acetylacetonate in trichlorobenzene at reflux temperature.
Magnetic properties of frozen solutions of highly oxidized iron porphyrin complexes were investigated by EPR and Mössbauer
spectroscopy. The Mössbauer spectra, recorded at low temperatures in various magnetic fields, were analyzed on the basis of
spin Hamiltonian simulations. Spin coupling between ferryl iron (FeIV) and porphyrin cation radical was...
Oxorhenium(V) porphyrins ReO(P)X (X = Cl, Br) or [ReO(P)]2O, or trichlororhenium(V) porphyrins ReCl3(P) (P = OEP, TPP, TTP, TAP, TCIP, TMP)2,3, respectively, are transformed into nitridorhenium(V) porphyrins ReN(P) with hydrazine hydrate in the presence of ethanol, in good yields. The diamagnetic complexes are stable towards hydrolysis and contain...
Further symmetrical cerium(IV) bisporphyrinates are prepared from cerium(III) acetylacetonate and tetraphenylporphyrin, tetra-p-chlorophenylporphyrin, and hexadecahydrotetrabenzporphyrin. In the latter case, a biscerium(III) triple-decker is also found which is the only product in the case of octamethylporphyrin. From a mixture of two different por...
The five-coordinate, high-spin (S = 2) (ethanethiolato)- and (tetrafluorobenzenethiolato)iron(II) "picket-fence" porphyrin derivatives [Fe(TPpivP)(SC2H5)][Na(C222)] (1), [Fe(TPpivP)(SC6HF4)][Na(C222)] (2), and [Fe(TPpivP)(SC6HF4)][Na(Cl8c6)] (3) have been synthesized and characterized. The X-ray structure of the chlorobenzene solvate of 1 has been...
