- Controlled microwave-assisted synthesis of metallophthalocyanines
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A controlled microwave-assisted strategy has been elaborated for the fast and efficient synthesis of metallophthalocyanines scaffold. Compared to the conventional protocol, reproducibility of products was achieved, accompanied by significantly high purity and excellent yields
- Seyyedhamzeh, Mozhdeh,Ganji, Nasim,Shaabani, Ahmad
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- Iron phthalocyanine as new efficient catalyst for catalytic transfer hydrogenation of simple aldehydes and ketones
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Catalytic transfer hydrogenation (CTH) of various aldehydes and ketones was studied using iron phthalocyanine catalyst, in order to substitute the typically used rare transition metals (Ir, Rh, Ru) with an easily available and less expensive metal. Iron phthalocyanine was found to be an efficient hydrogenation catalyst and its immobilized version was successfully prepared. The immobilized iron phthalocyanine was also active in the CTH reaction of various carbonyl compounds, and it was easy to handle and possible to recycle.
- Bata, Pter,Notheisz, Ferenc,Kluson, Peter,Zsigmond, gnes
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- SYNTHESIS OF METALLOPHTHALOCYANINES FROM PHTALONITRILE WITH STRONG ORGANIC BASES
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Several metallophthalocyanines (MPc: M=Ni(II), Co(II), Zn(II), Pb(II), Fe(II), Sn(II), Cd(II), Mg(II), and Mn(III)) were obtained by heating phthalonitrile with metal salts in alcohols in the presence of 1,8-diazabicycloundec-7-ene.Metal acetylacet
- Tomoda, Haruhiko,Saito, Shojiro,Shiraishi, Shinsaku
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- One-step photocatalytic benzene hydroxylation over iron (II) phthalocyanine: A new application for an old catalyst
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In the present study, iron (II) phthalocyanine was introduced as an effective and recyclable photocatalyst for direct hydroxylation of benzene to phenol as a model reaction under photocatalytic conditions at ambient temperature. The effect of different parameters such as solvent, concentration of the oxidant, irradiation time, and amount of the catalyst was investigated. Acetonitrile was selected as the optimum solvent, where hydrogen peroxide plays the role of the oxidant which is considered as an eco-friendly process. The results not only showed a 15.2 % yield of phenol at a selectivity of higher than 99 % under optimized condition but also exhibited a highly stable and reusable behavior. The catalyst was thoroughly characterized by UV–vis spectroscopy, Fourier transform infrared spectroscopy (FT-IR), field emission electron microscopy (FE-SEM), high-resolution transmittance electron microscopy (HR-TEM), X-ray diffraction (XRD), nitrogen adsorption-desorption isotherm (BET), and X-ray photoelectron spectroscopy (XPS). Density-Functional Tight-Binding (DFTB+) calculation was used to study the catalyst transition energy on the Materials Studio software.
- Asghari, Saeid,Farahmand, Shohreh,Razavizadeh, Jalal. S.,Ghiaci, Mehran
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- Synthesis, thermal stability and structural characterisation of iron(II) phthalocyanine complex with 4-cyanopyridine
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A new complex of bis-axially coordinated iron(II) phthalocyanine by 4-cyanopyridine (4-CNpy) has been obtained in crystalline form as an adduct with two 4-CNpy molecules. The [FePc(4-CNpy)2] · 2(4-CNpy) crystallises in the monoclinic system, space group P21/c with two molecules in the unit cell. The iron(II) coordinates four isoindole nitrogen atoms of the almost planar phthalocyaninato(2-) macroring and axially two nitrogen atoms of 4-CNpy molecules. The coordination polyhedron around the Fe(II) atom approximates to a tetragonal by-pyramid. Four equatorial Fe-N bonds are shorter (1.936(2) A?) than two axial Fe-N bonds (2.027(2) A?). The centrosymmetric FePc(4-CNpy)2 molecules form alternating sheets parallel to the bc crystallographic plane and solvated 4-CNpy molecules that are anti-parallel oriented by their polar cyano groups are located between the sheets of FePc(4-CNpy)2 molecules. Ligation of the intermediate-spin iron(II) phthalocyanine by 4-CNpy molecules leads to the low spin Fe(II) complex. The importance of the d(π) → π*(Pc) back donation is manifested in the difference between the values of C-N isoindole and C-N azamethine bond lengths of the Pc macrocycle. The thermal analysis of the crystals of [FePc(4-CN)2] · 2(4-CNpy) shows two steps responsible for a loss of solvated (～170 °C) and coordinated (～235 °C) 4-CNpy molecules.
- Janczak, Jan,Kubiak, Ryszard
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- Bio-inspired iron/sulfur/graphene nanocomposite and its use in the catalysis of the oxygen reduction reaction at room temperature in alkaline media on a glassy carbon electrode
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This work demonstrates the performance of a bio-inspired iron/sulfur/graphene nanocomposite as a non-platinum electrocatalyst for the oxygen reduction reaction (ORR) in an alkaline medium. The catalyst shows the most positive ORR onset potential (1.1 V vs. RHE) according to its unique structure in the alkaline medium (KOH solution, pH = 13) at low temperature (T = 298 K). The catalyst is evaluated by the rotating-disk electrode (RDE) method under various rotating speeds (0–2,000 rpm) in the potential range ?0.02–1.18 V vs. a rechargeable hydrogen electrode (RHE). The number of transferred electrons, as one of the most important parameters, is almost constant over a wide range of potentials (0.1–0.8 V), which indicates a more efficient four-electron pathway from O2 to H2O on the FePc-S-Gr surface. The mean size of catalyst centers are in the nanoscale (1/2 of FePc-S-Gr displays a negative shift of only 7.1 mV after 10,000 cycles.
- Seyyedi, Behnam,Ahmadi Variani, Bahar,Habibi, Esmaeil
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- CARBONYL DERIVATIVES OF PHTHALOCYANINATOIRON(II), ESPECIALLY THOSE CONTAINING GROUP VI AXIAL DONOR ATOMS. CRYSTAL AND MOLECULAR STRUCTURE OF CARBONYL(N,N-DIMETHYLFORMAMIDE)PHTHALOCYANINATOIRON(II) AND MOESSBAUER STUDIES OF SOME OF THE PRODUCTS
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The carbonyl adduct of phthalocyaninatoiron(II), FePc, with N,N-dimethylformamide (DMF) as axial ligand, FePc(CO)DMF, was prepared by the reaction of iron carbonyls, Fe(CO)5 or Fe2(CO)9, with o-phthalonitrile in DMF as solvent.Several carbonyl adducts of FePc of general formula FePc(CO)L are reported, with L being a ligand with oxygen, sulphur and nitrogen donor atoms (L = tetrahydrofuran, H2O, CH3OH, dimethylsulphoxide, tetrahydrothiophene, ammonia, n-propylamine, diethylamine, triethylamine).The crystal and molecular structure of FePc(CO)DMF*DMF was investigated byX-ray diffraction methods.The compound has a monoclinic unit cell and space group P21/n, a 9.86(1), b 17.35(3), c 19.79(4) Angstroem, β 87.9(2) deg, Z = 4, U 3383 Angstroem3, Dc 1.458 g cm-3.The iron atom is hexacoordinated to the four inner nitrogen atoms of the macrocycle, to carbon monoxide (Fe-C distance 1.72(2) Angstroem) and to DMF (Fe-O distance 2.07(1) Angstroem).The extra DMF occupies lattice sites.All of the compounds reported in this paper are substantially diamagnetic.Moessbauer spectra show typical isomer shift parameters for the bis-adducts and for the carbonyl adducts, substantially independent of the nature of the axial ligand.The quadrupole splitting parameter of the carbonyl adducts is strongly affected by the nature of the axial ligand.
- Calderazzo, Fausto,Pampaloni, Guido,Vitali, Dario,Pelizzi, Giancarlo,Collamati, Ines,et al.
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- Reactions of ferrocene with phthalonitrile on the surface of oxide powders
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The reaction of ferrocene with phthalonitrile at 200°C in a vacuum in the absence of solvents forms crystals of the monoclinic phthalocyanine β phase and ferrocene polymerization products. The use of oxide powders (SiO 2, V2O5) as a surface for the reaction of ferrocene with phthalonitrile makes it possible to obtain iron phthalocyanines. The samples of pure compounds and deposited phthalocyanine complexes were analyzed by electronic absorption and IR spectroscopy, and X-ray diffraction. Pleiades Publishing, Inc., 2006.
- Suvorova,Verle,Bazyakina,Kutyreva,Makarov,Shchupak
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- Systematic study of transition-metal (Fe, Co, Ni, Cu) phthalocyanines as electrocatalysts for oxygen reduction and their evaluation by DFT
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In this work, a facile approach is reported to prepare a series of transition-metal phthalocyanines (TMPc) supported on graphitized carbon black (TMPc/GCB, TM: Fe, Co, Ni and Cu) as oxygen reduction reaction (ORR) electrocatalysts, via π-π interaction self-assembly. Through transmission electron microscopy (TEM), Raman spectroscopy and UV spectroscopy, it was found that TMPc was coated on graphitized carbon black with non-aggregated morphology. The catalytic activity, both in terms of the onset potential (0.98 V to 0.76 V) and half-wave potential (0.90 V to 0.55 V) follows the trend of FePc/GCB > CoPc/GCB > CuPc/GCB > NiPc/GCB. However, the catalytic durability follows the decreasing order of NiPc/GCB > CoPc/GCB > FePc/GCB > CuPc/GCB. To better elucidate the ORR catalytic mechanism for TMPc/GCB, we employed density functional theory (DFT) calculations and drew the following conclusions: (i) the -O2 adsorption is the major step to determine the ORR catalytic activity; (ii) the way O2 is adsorbed on TMPc is the key point affecting the Tafel slope; (iii) the -H2O2 desorption determines the transfer electron number; and (iv) the -OH desorption and the central metal atom removal leads to the damage affecting catalytic durability.
- Zhang, Zhengping,Yang, Shaoxuan,Dou, Meiling,Liu, Haijing,Gu, Lin,Wang, Feng
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- Improved performance of organic light-emitting diodes using a metal-phthalocyanine hole-injection layer
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In this paper, we systematically investigated the physical characteristics of the various metal phthalocyanines (MPcs) and the influence of the MPcs hole-injection layer on the electroluminescence performance of indium tin oxide/MPc/naphthylphenylbiphenyl diamine (NPB)/ Al q3 LiFAl devices. The characteristics were measured at room temperature with a thickness variation of the MPc layer. The individual highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO) energies of MPcs were derived from the photoelectron emission and the optical absorption measurements. The results showed that the HOMO and LUMO level energies of MPcs are dependent on their central metal atoms. The turn-on voltage for the devices is lowered by inserting MPc layers and remains virtually the same as the MPc layer thickness is adjusted in the range of 5-15 nm. In addition, the turn-on voltage decreases significantly with the increase of the HOMO levels of the MPc films, demonstrating that the MPc/NPB interface instead of the ITO/MPc interface plays an important role in the hole injection.
- Kao, Po-Ching,Chu, Sheng-Yuan,Liu, Shyh-Jiun,You, Zong-Xian,Chuang, Chan-An
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- Backscatter Fe-57 M?ssbauer studies of iron(II) phthalocyanine
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Phthalocyanines are established gas sensitive materials. We have successfully recorded backscatter conversion electron M?ssbauer spectra (CEMS) of iron(II) phthalocyanine. Further, we have shown that the introduction of nitrogen dioxide, a typical analyte for these materials, into the detector system can be achieved without deleterious effects. The method allows surface sensitive spectra of these materials to be recorded under normal sensor operating conditions of temperature and pressure. The high vacuum conditions of other surface sensitive techniques used to study materials of this type are not required by this method.
- Bell, Norman A.,Brooks, John S.,Forder, Susan D.,Robinson, Jacqueline K.,Thorpe, Stephen C.
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- Cobalt(II), copper(II), and iron(II) tetrasulfophthalocyanines covalently supported on wool: Synthesis, characterization and catalytic activity
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Functionalized wool with cobalt(II), copper(II), and iron(II) tetrasulfophthalocyanine (CoTSPc@wool, CuTSPc@wool, and FeTSPc@wool) have been synthesized and their structures characterized by flame atomic absorption spectroscopy (FAAS), FT-IR, UV-vis, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and the energy dispersive spectroscopy (EDS) analysis. The catalytic activity of the synthesized catalysts was investigated for the aerobic oxidation of alkyl arenes and alcohols to their corresponding carbonyl compounds in the absence of any co-promoter and additional oxidizing reagent. We found the best catalyst for the mentioned reactions is the CoTSPc@wool from the solvent, conversion, temperature, and reaction time point of views. The synthesized catalysts can be readily recycled and reused for several runs without significant loss of efficiency.
- Shaabani, Ahmad,Hezarkhani, Zeinab
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- UEBER DIE NATUR DER UEBERGANGSMETALL-KOHLENSTOFF-?-BINDUNG. X. UEBER DIE DARSTELLUNG, CHARAKTERISIERUNG UND THERMISCHE ZERSETZUNG VON BIS(η5-CYCLOPENTADIENYL)TITAN-BIS(THIOANISOLYL) UND NATRIUM-THIOANISOLYLPHTHALOCYANINATO-FERRAT(II)*4THF
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Cp2TiCl2 (Cp = η5-C5H5; H2Pc = phthalocyanine) reacts with 1.9 equivalents of PhSCH2Li to give Cp2Ti(CH2SPh)2 (I), the structure of which follows from the results of elemental analysis, 1H NMR and mass spectroscopic investigations and proptolysis to form PhSCH3.I decomposes in toluene at 100 degC, with the methylene group being liberated to form 2 (II) (ca. 31percent) and Cp2Ti(SPh)2 (III) (ca. 16percent).Na*4THF (IV) (μeff. 0.12 BM) has been obtained as green-black, air-sensitive crystals in an oxidative addition reaction from PhSCH2Cl and iron(0) phthalocyanine.In boiling THF the organyl group is gradually split off without formation of a considerable amount of the corresponding thiophenolato complex.The results are in agreement with the assumption that the formation of an η2-thioanisolyl structure as an unstable intermediate is essentially important for the conversion of the thioanisolyl into the thiophenolato complexes.
- Steinborn, Dirk,Taube, Rudolf
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- High-pressure Conditions for Improved Synthesis of Phthalocyanines
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Improved rates of formation and yields of phthalocyanines are observed when the reaction between phthalonitrile and a metal salt is carried out at pressures around 10 kbar.The reaction also benefits from the presence of a superbase, 1,5-diazabicyclonon-5-ene or 1,8-diazabicycloundec-7-ene, and a reducing agent, hydroquinone.In addition to providing superior yields of metallophthalocyanoines from a variety of metal salts, these improvements permit the synthesis of phthalocyanines otherwise difficult to obtain.High pressure combinated with a reducing agent is particularly advantageous.In the absence of a metal salt, good yields of metal-free phthalocyanine were obtained.
- Edmondson, Stephen J.,Hill, Jon S.,Isaacs, Neil S.,Mitchell, Philip C. H.
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- Synthesis of 1-alkynyl(phthalocyaninato)iron(II) and -ruthenium(II) complexes
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The preparation of dilithiumiron(II) (IIIb) is described.For comparison dilithiumiron(II) (IIIa) was also made.Several 1-alkynyl(phthalocyaninato)ruthenium(II) co
- Hanack, Michael,Knecht, Siegfried,Schulze, Hans-Joachim
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- A simple synthesis of symmetric phthalocyanines and their respective perfluoro and transition-metal complexes
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We report a simple synthesis protocol for making phthalocyanines (Pcs) starting from phthalonitriles. This method is general and requires no specialised equipment. The complexes are isolated and characterised using X-ray diffraction, NMR, FTIR and Raman spectroscopy and high-resolution mass spectrometry. First, we study and present a one-step synthesis route to a metal-free Pc (H2PcH16), as well as to the corresponding MPcH16 complexes of Mn, Fe, Co, Ni, Cu and Zn. Then, we show that this route can also be used to make the fluorinated Pc analogues (MPcF16). Finally, we present a new and useful procedure for inserting a metal ion into a metal-free H2PcH16 ring, by direct metalation, yielding the corresponding MPcH16 complex. This last method is especially useful if you want to make different MPcH16 complexes.
- Denekamp, Ilse M.,Veenstra, Florentine L.P.,Jungbacker, Peter,Rothenberg, Gadi
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- Effects of MN4-Type Coordination Structure in Metallophthalocyanine for Bio-Inspired Oxidative Desulfurization Performance
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Oxidative desulfurization (ODS) is the promising new method for super deep desulfurization of fuel oil. The oxidative desulfurization performance of the metal-N4-chelates metallophthalocyanines (MPcs) is related to the chemical properties of conjugate structures and the central metal ions. Herein, a biomimetic catalytic system composed of metallophthalocyanines (MPcR4, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II); R = -H, -COOH, -NO2, -NH2) and molecular O2 was performed to study the influence of MN4-type coordination structure in metallophthalocyanines for the degradation of dibenzothiophene (DBT) in model oil containing n-octane. The results reveal that the conjugate structures and the center metal ions of metallophthalocyanines played key roles in oxidative desulfurization performance. The inductive effect of different R substituents strongly affected the electron cloud distribution of the conjugate structures and the catalytic performance. Moreover, the catalytic activity of MPcs, which is related to the d electronic configuration and ligand-field effects, does not sequentially increase with the increase in the d electron number of central metal ions.
- Tan, Amin,Tian, Min,Yang, Yan,Zhang, Gai,Zhang, Yufan
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- Nano magnetite supported phthalocyanine complexes of Cu(II) and Fe(II) as new heterogeneous effective catalysts for synthesis of β-amido ketones
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In this study, a novel, heterogeneous and reusable catalyst prepared by the coordinative anchoring of metal(II) phthalocyanine complexes (M: Fe, Cu) on the guanidine-functionalized magnetic nanoparticles was reported. The synthesized catalysts were characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), vibrating sample magnetometer (VSM), thermal gravimetric analysis (TGA), and FT-IR measurements. The catalysts were used successfully in the synthesis of β-amido ketones. This method provides several advantages including little catalyst loading, absence of any tedious workup or purification and at least six times reusability of the catalyst without any remarkable change in the catalytic activity. (Figure presented.).
- Naeimi, Hossein,Rahmatinejad, Soraya
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p. 4210 - 4227
(2019/01/19)
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- Transition metal-free 1,3-dimethylimidazolium hydrogen carbonate catalyzed hydration of organonitriles to amides
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An efficient hydration of organonitriles to the corresponding amides was accomplished using 1,3-dimethylimidazolium hydrogen carbonate as an organocatalyst. The developed catalytic method was also applicable for the synthesis of metal phthalocyanines.
- Verma, Praveen Kumar,Sharma, Upendra,Bala, Manju,Kumar, Neeraj,Singh, Bikram
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p. 895 - 899
(2013/04/23)
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- Cobalt(II) phthalocyanine-catalyzed highly chemoselective reductive amination of carbonyl compounds in a green solvent
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Cobalt phthalocyanine has been employed for the highly chemoselective reductive amination of aldehydes and ketones in ethanol as a green solvent. A large range of functional groups such as nitro, acid, amide, ester, nitrile, halogen, lactone, methoxy, hydroxy, alkene, N-benzyl, O-benzyl and heterocyclic rings were well tolerated under the present reaction conditions. Copyright
- Kumar, Vishal,Sharma, Upendra,Verma, Praveen K.,Kumar, Neeraj,Singh, Bikram
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supporting information; experimental part
p. 870 - 878
(2012/05/04)
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- Effect of N atoms in the backbone of metal phthalocyanine derivatives on their catalytic activity to lithium battery
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Metal phthalocyanine (MPc, M = Mn2+, Fe2+, Co2+, Ni2+ and Cu2+), metal tetrapyridinoporphyrazine, and metal tetrapyrazinoporphyrazine are synthesized by microwave reaction and characterized by elemental analyzer, IR spectroscopy and UV-vis spectroscopy. The catalytic activity of MPc derivatives to Li/SOCl2 battery is evaluated by the relative discharge energy of the battery whose electrolyte contains the compounds. The discharge energy of Li/SOCl2 battery catalyzed by MPc is approximately 0-61% higher than that of Li/SOCl2 battery in the absence of compounds, depending on the central metal ion. To the same central metal ion, the discharge energy of Li/SOCl2 battery catalyzed by MTAP is approximately 60% higher than that by MPc. The discharge energy of Li/SOCl2 battery in which SOCl2 contains MPTpz is approximately 17-19% higher than that of the battery in the absence of compounds, and almost independent of central metal ions. It shows a correlation existing between the structure and the catalytic active sites of MPc derivatives. The double active site model is proposed to interpret the results.
- Xu, Zhanwei,Zhang, Guoxiang,Cao, Zeyuan,Zhao, Jianshe,Li, Hejun
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p. 101 - 105
(2010/06/16)
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- Stereochemistry and properties of the M(II)-N(py) coordination bond in the low-spin dipyridinated iron(II) and cobalt(II) phthalocyanines
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A comparison between the coordination bond M(II)-N(py) and vibrational properties and stereochemistry of the dipyridinated iron(II) and cobalt(II) phthalocyaninato complexes, FePc(py)2 and CoPc(py)2 (Pc=C32H16N8, py=C5H5N), is carried out using the single crystal X-ray diffraction and the vibrational spectroscopy. Both dipyridinated complexes have been synthesized in crystalline form by heating of the β-FePc or β-CoPc in pyridine at 160°C. The crystals are formed during the slowly cooling process. The crystal of FePc(py)2 and CoPc(py)2 are isostructural. They crystallize in the space group P21/c of the monoclinic system with two molecules per unit cell. The structural results and coordination bond properties are strictly related in these complexes. The Fe2+ and Co2+ cations are coordinated by four N-isoindole atoms of the phthalocyaninato(2-) macrocycle and axially by two nitrogen atoms of pyridine molecules to form a tetragonal bypyramid. The vibrational M-Nisoindole parameters are much more affected than the corresponding structural parameters by the difference in the electronic structure of the Co and Fe. The axial M(II)-N(py) bond length depends strongly on the electron configuration of the central metal. The value of the M(II)-N(py) bond length of 2.039(2) A? in FePc(py)2 and 2.340(2) A? in CoPc(py)2 clearly evidences on the localization of the unpaired electron on the dz2 orbital of the Co in the cobalt complex. The electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility measurements have also detected the unpaired electron in the molecule of CoPc(py)2. EPR and magnetic susceptibility measurements performed on a solid sample of FePc(py)2 shown on its diamagnetic character. The importance of the d(π)→π*(Pc) back donation is manifested in the difference between the values of the C-Nisoindole and C-Nazamethine bond lengths of the Pc macrocycle.
- Janczak, Jan,Kubiak, Ryszard
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- Multistep electron transfer in palladium-catalyzed aerobic oxidations via a metal macrocycle-quinone system
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Selective palladium-catalyzed aerobic conditions of olefins and conjugated dienes with the aid of a metal macrocycle-quinone system have been developed. This involves a multistep electron transfer with three catalysts (Pd(OAc)2, hydroquinone, metal macrocycle). The triple catalytic system was applied to (i) 1 ,4-oxidation of conjugated dienes (1,4-diacetoxylation and 1,4-dialkoxylation), (ii) oxidation of terminal olefins to ketones, and (iii) allylic oxidation of cyclic olefins to 2-alken-1-yl acetates. The reactions occur under very mild conditions, (i) and (ii) at room temperature and (iii) at 60 °C, and are reminiscent of aerobic processes occurring in living organisms. Thus, there is an electron transfer from the substrate to Pd(II) giving Pd(0), followed by another electron transfer from Pd(0) to benzoquinone. The hydroquinone thus formed transfers electrons to the oxidized form of the metal macrocycle, which is reduced. The latter is reoxidized by electron transfer to molecular oxygen. A number of metal macrocycles such as metal(salen) complexes Co(salophen), Co(TPP), and iron phthalocyanine (Fe(Pc)) were tested as oxygen-activating complexes. In the 1,4-diacetoxylation of 1,3-dienes, and in the allylic oxidation, several of these metal macrocycles gave good results. In the 1,4-dialkoxylation of 1,3-dienes and in the oxidation of terminal olefins to ketones, which occur in the presence of a strong acid, only Fe(Pc) survived the reaction conditions.
- B?ckvall, Jan-E.,Hopkins, R. Bruce,Grennberg, Helena,Mader, Mary M.,Awasthi, Alok K.
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p. 5160 - 5166
(2007/10/02)
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- iron(II) Compounds with Isocyanides as Axial Ligands
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Aliphatic and aromatic monodentate isocyanides RNC (R = t-Bu, c-Hx, substituted Ph) react with iron(II) (TPyPFe) to form the corresponding diaxially substituted iron(II) compounds TPyPFe(RNC)2 1a-8a.The spectroscopic data and thermal properties of the complexes are described and compared with the analogous PcFe(CNR)2 compounds 1b-8b.
- Hanack, Michael,Thies, Ruediger
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p. 1225 - 1230
(2007/10/02)
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- Oxochromium compounds. 1. Synthesis and properties of μ-oxo chromium-iron porphyrin and phthalocyanine compounds
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The reaction between CrIVO(P) and FeII(P′) leads to the formation of μ-oxo heterobinuclear complexes (P)CrOFe(P′) where P and P′ represent dianions of porphyrins that may be the same or different. [Abbreviations for the dianions of 5,10,15,20-tetraarylporphyrins: TPP, tetraphenylporphyrin; TTP, tetra-p-tolylporphyrin; TMP, tetrakis(p-methoxyphenyl)porphyrin; TFP, tetrakis(p-fluorophenyl)porphyrin; TCP, tetrakis(p-chlorophenyl)porphyrin; TXP, tetra-3,5-xylylporphyrin; OEP, the dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin; Pc, the dianion of the phthalocyanine molecule.] The complexes react with heterocyclic Lewis bases, and these coordinate to Cr only. The visible, infrared, 1H NMR, and Mo?ssbauer spectra are reported for the compounds. The variation of magnetic susceptibility with temperature down to 4.2 K is interpreted in terms of strong antiferromagnetic coupling between Cr(III) (S = 3/2) and Fe(III) (S = 5/2) centers with J values in the range -130 to -150 cm-1. Zero field splitting effects are important at low temperatures. The reaction of CrO(TPP) with FeII(Pc) forms an analogous μ-oxo complex having porphyrin and phthalocyanine groups attached to Cr(III) and Fe(III), respectively.
- Liston, David J.,Kennedy, Brendan J.,Murray, Keith S.,West, Bruce O.
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p. 1561 - 1567
(2008/10/08)
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- Cyanide Containing Phthalocyaninatoiron Compounds: Synthesis and Electrical Conductivities
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The preparation of cyanide containing phthalocyaninatoiron(II) or -iron(III) derivatives either with terminal or bridging cyanide is described.With help of the CN valence frequency (IR) and the magnetism of the compounds the oxidation state of the iron is determined.Thermoanalytical and electrical conductivity data are reported. - Key words: (μ-Cyano)phthalocyaninatoiron(II), -iron(III), Thermal Analysis, Electrical Conductivity
- Schneider, Otto,Hanack, Michael
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p. 265 - 268
(2007/10/02)
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- Axially Polymerized (Phthalocyaninato)iron(II) with Pyrazine, 4,4'-Bipyridine, 1,4-Diisocyanobenzene, or 1,4-Diazabicyclooctane as Bridging Ligands; Synthesis, Characterization, and Electrical Conductivities
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(Phthalocyaninato)iron(II), PcFe, reacts with the bidentate ligands L = pyrazine, 4,4'-bipyridine, 1,4-diisocyanobenzene, and 1,4-diazabicyclooctane in appropriate solvents to produce the polymers n (1a-d).These are the first axially polymerized phthalocyaninato transition metal complexes containing bridging ligands capable of conjungation.In the presence of excess liquid ligands the monomeric PcFeL2 complexes 2a-k are formed.The polymers 1a-d and the monomers 2a-k were investigated and characterized in detail by IR/FIR and UV/VIS/NIR spectra.The structures of soluble PcFeL2 complexes were determined by 1H and 13C NMR spectroscopy.The thermal stabilities of these compounds were measured by means of TG/DTG/DTA.The polymers 1a-c show conductivities of ?295 K = 10-5 S x cm-1 which are up to 107 times greater than the conductivities of the monomers 2a,g, and k.The conductivities of the polymers are discussed with respect to their structural features.
- Schneider, Otto,Hanack, Michael
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p. 2088 - 2108
(2007/10/02)
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- Electrosynthesis and Resonance-Raman Spectrum of Phthalocyaninatoiron(II)
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The electrosynthesis of phthalocyanine complexes of iron, cobalt, nickel, and copper has been carried out and the method provides a facile, one-stage, room-temperature preparation.The electronic and i.r. spectra have been studied for all four complexes and resonance-Raman data are presented also for dissolved in aniline.Excitation profiles based on the electronic absorption band of at 606 nm suggest that this electronic absorption is a vibronic shoulder on the side of the main electronic (0-0) transition at 668 nm.
- Griffiths, Lynne,Straughan, Brian P.,Gardiner, Derek J.
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p. 1193 - 1196
(2007/10/02)
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