bluuebunny/crossref_metadata_2025_split huggingface dataset:
Grain‐size dependence of absorption characteristics of the electromagnetic wave absorbers of ferrite‐SiO2 composites
Authors: Kusunoki Hiroki , Kondo Takatoshi , Hiraki Kiyohiro , Takada Kazushi , Yoshikado Shinzo 
Published: January 2004

AbstractGrain‐size dependence of electromagnetic absorbing characteristics for composite materials made of Ni‐Zn ferrite and SiO2 was investigated using SiO2 with various grain sizes (29 µm, 30 nm, 12 nm, and 7 nm). The absorption characteristics of ferrite composites using SiO2 with an average grain size of 30, 12, or 7 nm were improved compared with those of ferrite composites using SiO2 with an average grain size of 29 µm in the low‐frequency region. Furthermore, the grain size dependence of the absorption characteristics for composite materials of Mn‐Zn ferrite with an average grain size of 130 nm and SiO2 with an average grain size of 29 µm was investigated. The absorbing center frequency shifted to a higher frequency region than that of Mn‐Zn ferrite. © 2004 Wiley Periodicals, Inc. Electr Eng Jpn, 146(4): 1–9, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.10269
Access to 3‐Methyl‐4‐methylene‐N‐tosylpyrrolidine and 3,4‐DimethylN‐tosylpyrroline by Ruthenium‐Catalyzed Cascade Cycloisomerization/Isomerization Reactions
Authors: Özdemir Ismail , Çetinkaya Engin , Çetinkaya Bekir , Çiçek Metin , Sémeril David , Bruneau Christian , Dixneuf Pierre H. 
Published: January 2004

AbstractNew RuCl2(benzimidazole)(arene) complexes have been prepared. Upon reaction with 1,1‐diphenylprop‐2‐ynol they generate catalyst precursors which perform the cycloisomerization of diallyltosylamide into 3‐methyl‐4‐methylene‐N‐tosylpyrrolidine. The presence of N‐(2,4,6‐trimethylbenzyl)benzimidazole as ligand leads to a subsequent isomerization and gives the 3,4‐dimethyl‐N‐tosylpyrroline. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Heterometallic Molecular Squares and Polymers Based On Self‐Assembly Reactions of Multiply Bonded Dirhenium Complexes
Authors: Bera Jitendra K. , Bacsa John , Smucker Bradley W. , Dunbar Kim R. 
Published: January 2004

AbstractSelf‐assembly reactions of the triply‐bonded dirhenium complex cis‐[Re2Cl2(dppm)2(O2CC5H4N‐4)2] with cis‐protected PtII and ZnII precursors have produced heterometallic squares. Analogous reactions with Ag(O3SCF3), cis‐[Re2Cl4(O2CCH3)2(H2O)2] and [Rh2(O2CCH3)4] have yielded mixed‐metal polymeric structures. These results demonstrate that the isonicotinate ligand is useful for accessing heterometallic structures involving metal−metal bonded complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Synthesis and X‐ray Crystal Structures of Cobalt and Copper Complexes of 1,3‐Bis(benzotriazolyl)propanes
Authors: Børsting Philip , Steel Peter J. 
Published: January 2004

AbstractTwo propylene‐bridged bis‐benzotriazole ligands,1and2, were used to obtain three novel coordination polymers with cobalt(II), copper(II) and copper(I). The complexes were structurally characterised by X‐ray crystallography. The complex [Co(1)Cl2]n,3, possesses a helical zigzag chain structure in which tetrahedral CoCl2centres are bridged by molecules of1having an extended conformation. The complex [Cu(1)Cl2]n,4, exhibits a more complex supramolecular architecture, which extends in two dimensions, with bridging through Cu2Cl4dimeric units in one direction and through the organic ligand in an orthogonal direction. The complex [Cu(2)Cl]n,6, has a one‐dimensional polymeric structure involving 16‐membered M2L2rings bridged by Cu2Cl2units. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Spectroscopic Characterization of an FeIV Intermediate Generated by Reaction of XO− (X = Cl, Br) with an FeII Complex Bearing a Pentadentate Non‐Porphyrinic Ligand − Hydroxylation and Epoxidation Activity
Authors: Balland Véronique , Charlot Marie‐France , Banse Frédéric , Girerd Jean‐Jacques , Mattioli Tony A. , Bill Eckhard , Bartoli Jean‐François , Battioni Pierrette , Mansuy Daniel 
Published: January 2004

AbstractMononuclear FeIV intermediates have been generated in MeOH upon reaction of sodium hypochlorite or hypobromite with a ferrous complex bearing the pentadentate ligands N‐methyl‐N,N′,N′‐tris(2‐pyridylmethyl)ethane‐1,2‐diamine (L52) or N‐methyl‐N,N′,N′‐tris(2‐pyridylmethyl)propane‐1,3‐diamine (L53). These highly unstable green complexes are characterized by an absorption band at ca. 750 nm. Mössbauer data indicate that the iron center is low spin (S = 1) with an axial electronic structure, allowing identification of the mononuclear FeIV complexes as [L5FeIVO]2+ or [L5FeIVOCH3]3+. In acetonitrile/dichloromethane solutions, the L53FeIV system exhibits very selective activities toward hydroxylation of cyclohexane or epoxidation of cyclooctene and cis‐stilbene. Computational studies performed on [L5FeIVO]2+ and on the model compound [(NH3)5FeIVO]2+ reveal that the ground state possesses two unpaired electrons in the two π* orbitals, as known for O2. Electronic spectra computed by time‐dependent DFT exhibit only one band in the visible region that is essentially due to d‐d transitions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Phenylcyanamido Ligand Building Molecular, 1‐D, and 2‐D Systems − Syntheses, Crystal Structures and Magnetic Properties
Authors: Escuer Albert , Sanz Núria , Mautner Franz A. , Vicente Ramon 
Published: January 2004

AbstractSeveral MnII compounds have been synthesised with the phenylcyanamido ligand, C6H5−NCN−, and characterised by means of single crystal X‐ray structure determination. The reported compounds show a wide variety of nuclearity: mononuclear, dinuclear, 1‐D, and 2‐D compounds are present in which the phenylcyanamido anion (pcyd−) acts as a bridging ligand. The mononuclear compound [Mn(pcyd)2(phen)2] (1) crystallises in the orthorhombic system, Pbcn space group; dinuclear compound [{Mn(pcyd)(phen)(MeOH)}2(μ1,3‐pcyd)2] (2) crystallises in the monoclinic system, C2/c space group; 1‐D chain [Mn(4‐bzpy)2(μ1,3‐pcyd)2]n·MeOH (3·MeOH) crystallises in the triclinic system, P$\bar 1$
space group; 2‐D network [Mn(μ1,3‐pcyd)2(μ‐4,4′‐bpy)]n·MeOH (4·MeOH) crystallises in the monoclinic system, C2 space group. Susceptibility measurements on compounds 2−4 reveal moderate AF coupling in all cases. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Reduction of 1,2‐Bis[(2,6‐diisopropylphenyl)imino]acenaphthene (dpp‐bian) with Alkali Metals − A Study of the Solution Behaviour of (dpp‐bian)n−[M+]n (M = Li, Na; n = 1−4) with UV/Vis, ESR and 1H NMR Spectroscopy
Authors: Fedushkin Igor L. , Skatova Alexandra A. , Chudakova Valentina A. , Cherkasov Vladimir K. , Fukin Georgy K. , Lopatin Mikhail A. 
Published: January 2004

AbstractAn excess of lithium or sodium in diethyl ether consistently reduces 1,2‐bis[(2,6‐diisopropylphenyl)imino]acenaphthene (dpp‐bian) to the mono‐, di‐, tri‐ and tetraanion, (dpp‐bian)n−[M+]n (M = Li, Na; n = 1−4). The process of reduction is easily observed by the change in colour of the solution, on going from the neutral ligand (yellow) to the monoanion (red), the dianion (green for Na or Li in Et2O; dark blue, followed by green, for Li in TMEDA), the trianion (brown) and the tetraanion (red‐brown). In each reduction the maximum of the absorption, caused by electron transition from the HOMO of the respective form (dpp‐bian)n− (n = 1−4), is shifted to the long‐wavelength region in comparison to the previously reduced state. The disproportionation reactions (dpp‐bian)1− ⇄ (dpp‐bian)0 + (dpp‐bian)2− and (dpp‐bian)2− ⇄ (dpp‐bian)1− + (dpp‐bian)3− take place in solution along with the reduction process, thus causing the presence of three reduced forms of the ligand at the same time in the first and second stages of the reduction. Paramagnetic (dpp‐bian)1− and (dpp‐bian)3− are characterised by ESR spectroscopy. For the diamagnetic forms (dpp‐bian)2− and (dpp‐bian)4− 1H NMR spectra were recorded. The complex [Li+(dpp‐bian)(TMEDA)] (1), which formed from the initial stage of the reduction of dpp‐bian with lithium metal in TMEDA, was isolated in a crystalline form and its molecular structure was determined by single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
A New Alternating Ferro‐Antiferromagnetic One‐Dimensional Azido‐Bridged (Arylazoimidazole)manganese(II), [Mn(TaiEt)(N3)2]n [TaiEt = 1‐Ethyl‐2‐(p‐tolylazo)imidazole], Exhibiting Bulk Weak Ferromagnetic Long‐Range Ordering
Authors: Ray Umasankar , Jasimuddin Sk. , Ghosh Barindra Kumar , Monfort Montserrat , Ribas Joan , Mostafa Golam , Lu Tian ‐Huey , Sinha Chittaranjan 
Published: January 2004

Abstract1‐Ethyl‐2‐(p‐tolylazo)imidazole [p‐Me−C6H4−N=N−C3H2N2− Et‐1; TaiEt], an unsymmetrical N,N′‐blocker, and azide (N3−), a versatile intermediary, coordinate to manganese(II) forming an alternating chain with the formula [Mn(TaiEt)(N3)2]n (1). The compound crystallizes in the triclinic P$\bar 1$
space group with a = 7.9297(7) Å, b = 9.5883(9) Å, c = 11.8366(11) Å, α = 103.555(2)°, β = 105.811(2)°, γ = 104.280(2)°, and Z = 2. The structure consists of neutral chains in which each manganese(II) center is alternately bridged by two end‐on and two end‐to‐end azide ligands. The unsymmetrical arylazo heterocycle chelator creates a strong distortion around the metal center [N−Mn−N′ bite 67.7°; Mn−N′(azo) distance 2.562 Å]. The magnetic properties of 1 have been investigated over the temperature range 2−300 K. Magnetic data are analyzed on the basis of an alternating ferro‐ and antiferromagnetic Heisenberg chain of the manganese(II) ions, described by the spin Hamiltonian H = −J1ΣS2iS2i+1−J2ΣS2i+1S2i+2. The J exchange parameters are 2.65 ± 0.12 cm−1 and −14.5 ± 0.15 cm−1, respectively. Magnetic studies at low temperatures indicate long‐range ordering (canting) with a remnant magnetism that vanishes above 40 K. The canting phenomenon has been studied by various techniques including an EPR spectroscopic investigation at different temperatures and appears to be due to the local distortion around each metal center and the π‐π stacking in the 3‐D network. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
New Vanadium(V) Complexes with Salicylaldehyde Semicarbazone Derivatives: Synthesis, Characterization, and in vitro Insulin‐Mimetic Activity − Crystal Structure of [VvO2(salicylaldehyde semicarbazone)]
Authors: Noblía Pabla , Baran Enrique J. , Otero Lucía , Draper Patricia , Cerecetto Hugo , González Mercedes , Piro Oscar E. , Castellano Eduardo E. , Inohara Toshifumi , Adachi Yusuke , Sakurai Hiromu , Gambino Dinorah 
Published: January 2004

AbstractThe new dioxo(semicarbazone)vanadium(V) complexes cis‐VO2L, where L = salicylaldehyde semicarbazone (L1), salicylaldehyde 4‐n‐butylsemicarbazone (L2), or salicylaldehyde 4‐(2‐naphthyl)semicarbazone (L3), have been synthesized, characterized by 1H and 13C NMR and FTIR spectroscopy and tested for bioactivity as potential insulin‐mimetic agents. All dioxovanadium(V) complexes exhibited essentially no in vitro insulin‐mimetic activity, but the VO2L2 complex developed activity in the presence of ascorbic acid, similar to that of vanadyl sulfate. The molecular structure of the novel complex VO2L1 has been solved by X‐ray diffraction methods. It crystallizes in the tetragonal space group P42/n with a = 12.7674(7), c = 11.5308(5) Å, and Z = 8. The vanadium atom is in a distorted square‐pyramidal coordination, with L1 acting as a tridentate ligand through its azomethyne nitrogen atom, carbonyl oxygen atom and deprotonated phenol oxygen atom. The coordination sphere is completed by two oxo ligands at cis positions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Syntheses, Structures, and Magnetic Properties of Copper(II) Complexes with 1,3‐[Bis(2‐pyridylmethyl)amino]benzene (1,3‐tpbd) as Ligand
Authors: Foxon Simon P. , Torres Gemma Romualdo , Walter Olaf , Pedersen Jens Zacho , Toftlund Hans , Hüber Martina , Falk Karsten , Haase Wolfgang , Cano Joan , Lloret Francesc , Julve Miguel , Schindler Siegfried 
Published: January 2004

AbstractThe dinuclear copper(II) complexes {[Cu2(1,3‐tpbd)(H2O)(OAc)2](ClO4)2}0.23{[Cu2(1,3‐tpbd)(H2O)2(OAc)](ClO4)3}0.77·0.77H2O (1), [Cu2(1,3‐tpbd)(H2O)2(OAc)2](ClO4)2·2H2O (2), and the tetranuclear copper(II) complex [Cu4(1,3‐tpbd)2(H2O)2(SO4)4]·8H2O (3) {1,3‐tpbd = 1,3‐bis[bis(2‐pyridylmethyl)amino]benzene} were synthesised and structurally characterised by X‐ray diffraction. Variable‐temperature (2.0−290 K) magnetic susceptibility measurements on these complexes as well as on the dinuclear copper(II) complex [Cu2(1,3‐tpbd)(H2O)2(ClO4)3]ClO4 (4) (whose structure was published earlier) were performed. In contrast to 2 and 3, significant ferromagnetic coupling with J = +9.3 cm−1 was observed for 4 (the Hamiltonian being defined as Hˆ = −J Sˆ1·Sˆ2). Density functional theory (DFT) calculations were used successfully for the interpretation of the ferromagnetic coupling observed in 4. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Synthesis, Crystal Structures, and Magnetic Properties of a Mono‐ and a Dinuclear Copper(II) Complex of the 2,4,6‐Tris(2‐pyridyl)‐1,3,5‐triazine Ligand
Authors: Glaser Thorsten , Lügger Thomas , Fröhlich Roland 
Published: January 2004

AbstractThe reaction of 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tptz) with Cu(BF4)2·3H2O and N,N‐bis(3‐aminopropyl)methylamine (Medpt) yielded the monomeric complex [(tptz)CuII(Medpt)](BF4)2·2MeOH (1) whereas reaction of tptz with CuCl2·2H2O yielded the dinuclear complex [{CuIICl2}(tptz){CuIICl2(MeOH)}] (2). The molecular structures of 1 and 2 were established by single‐crystal X‐ray diffraction studies. The copper ion in complex 1 is elongated octahedral with the nitrogen atoms of Medpt and the triazine nitrogen atom of tptz in the equatorial positions, and the two pyridyl nitrogen atoms of tptz in axial positions. The two CuII ions in complex 2 are bridged by tptz, coordinating to Cu1 in a terpyridine‐like fashion and to Cu2 in a bipyridine‐like coordination mode. The triazine nitrogen atom bound to Cu1 is coordinated in an equatorial position whereas the triazine nitrogen atom bound to Cu2 is situated in the apical position. The equatorial plane of Cu1 is coplanar with the 1,3,5‐triazine plane whereas the equatorial plane of Cu2 is perpendicular to the 1,3,5‐triazine plane. Intermolecular interactions in the solid state result in both compounds in “dimeric units” due to hydrogen bonding. Both complexes were investigated by variable‐temperature magnetic susceptibility measurements. Through‐space dipolar couplings and/or weak through‐bond interactions in complex 1 result in a small intermolecular antiferromagnetic interaction (J = −0.09 cm−1). The intramolecular exchange coupling in the dinuclear complex 2 is antiferromagnetic (J = −2.5 cm−1). This antiferromagnetic interaction was analyzed in view of the molecular structure considering spin‐polarization, superexchange and orbital‐orthogonality. A spin‐polarization pathway seems to be the leading contribution which does not involve the 1,3 bridging pathway. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
The “Rebound Controversy”: An Overview and Theoretical Modeling of the Rebound Step in C−H Hydroxylation by Cytochrome P450
Authors: Shaik Sason , Cohen Shimrit , de Visser Samuël P. , Sharma Pankaz K. , Kumar Devesh , Kozuch Sebastian , Ogliaro François , Danovich David 
Published: January 2004

AbstractC−H hydroxylation by the enzyme cytochrome P450 is one of Nature’s important and most ubiquitous processes. There is strong evidence that the mechanism proceeds by initial hydrogen abstraction, from the alkane, by the high‐valent iron−oxo species of the enzyme, followed by a rebound of the alkyl radical to form the ferric−alcohol product complex (the Groves “rebound” mechanism). Nevertheless, the “rebound” mechanism is still controversial due to the ultrashort radical lifetimes deduced from radical‐clock experiments. This review describes the main elements of the controversy and its updated resolution by theory, with an emphasis on the controversial rebound step. The theoretically derived model for alkane hydroxylation is found to involve two‐state reactivity (TSR). In TSR, radicals are produced on two different spin‐state surfaces, and thereafter they react differently; on the low‐spin surface, the rebound proceeds with no product rearrangement and the lifetime of the radicals is ultrashort (or zero), while on the high‐spin surface the barrier for rebound is substantial and the lifetime of the radical is sufficiently long that rearrangement may compete with product formation by rebound. A new valence‐bond model is developed to model the rebound barrier on the high‐spin surface and conceptualize its dependence on the nature of the alkyl radical. The possible intermediacy of carbocationic intermediates alongside radicals is discussed. It is shown that the TSR scenario provides a satisfactory rationale for the controversial findings in the field, and makes verifiable predictions. One of the predictions of TSR is that the ratio of unrearranged to rearranged products, [U/R], will be subject to an intrinsic isotope effect that is substrate‐dependent. This prediction and its possible verification by experiment are discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
New Complexes of Niobium(V) and Tantalum(V) with Monoanionic NNO Heteroscorpionate Ligands
Authors: Otero Antonio , Fernández‐Baeza Juan , Antiñolo Antonio , Tejeda Juan , Lara‐Sánchez Agustín , Sánchez‐Barba Luis , Rodríguez Ana M. 
Published: January 2004

AbstractA new synthetic route based on bis(3,5‐dimethylpyrazol‐1‐yl)acetic acid (Hbdmpza) (1) has afforded the alcohol 2,2‐bis(3,5‐dimethylpyrazol‐1‐yl)ethanol (Hbdmpze) in good yield. This alcohol and the related lithium compound [{Li(bdmpza)(H2O)}4] are excellent precursors for introducing these scorpionate ligands into transition metal complexes. For example, the lithium compound and Hbdmpze (the latter after prior addition of nBuLi) react with a solution of MCl5 (M = Nb, Ta) in THF to give, after stirring for 12 h at −70 °C, a solution from which the complexes [MCl4(κ3‐bdmpzx)] (x = a, M = Nb 2, Ta 3; x = e, M = Nb 4, Ta 5) have been isolated. When solutions of 2−5 in THF were stirred at ca. 20 °C for 48 h, the oxo complexes [MCl2(O)(κ3‐bdmpzx)] (x = a, M = Nb 6, Ta 7; x = e, M = Nb 8, Ta 9) were isolated. The structures of these complexes have been determined by spectroscopic methods and the X‐ray crystal structure of 8 has been established. Finally, a new class of heteroscorpionate‐metal complexes containing an alkoxide ligand has been prepared. Direct reaction of the complexes [MCl4(κ3‐bdmpza)] (M = Nb 2, Ta 3) with several alcohols gave the complexes [MCl3(κ3‐bdmpza)(OR)] (M = Nb, R = Me 10, Et 11, iPr 12, tBu 13; M = Ta, R = Me 14, Et 15, iPr 16, tBu 17) after the appropriate workup. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Synthesis, Characterization and Electrochemistry of the Novel Dawson‐Type Tungstophosphate [H4PW18O62]7− and First Transition Metal Ions Derivatives
Authors: Mbomekalle Israel‐Martyr , Keita Bineta , Lu Yu Wei , Nadjo Louis , Contant Roland , Belai Nebebech , Pope Michael T. 
Published: January 2004

AbstractFollowing the synthesis of pure [H4PW18O62]7− (PW18), its derivatives monosubstituted with M (M = MoVI, VIV, VV, MnII, FeIII, CoII, NiII CuII and ZnII) were obtained. All compounds were characterized by elemental analysis, IR, UV/visible and 31P NMR spectroscopy. Their cyclic voltammetry properties were studied as a function of pH and systematically compared with those of their analogs derived from the symmetrical species, [P2W18O62]6−(P2W18). Comparison of the two unsubstituted precursors revealed that the merging of the first two waves of the monophosphate occurred in a less acidic medium than for the diphosphate. The observations point to the higher basicity of the reduced forms of PW18 compared with those of P2W18. The fingerprint pattern observed for α2‐P2W17M derivatives in media of pH = 3 consisted of the splitting of the third W redox system into two one‐electron closely spaced waves which is in contrast to the same system in α1‐P2W17M. This peculiarity was also obtained for several of the present α2‐PW17M systems in media of pH = 3 and confirmed that α2‐substituted derivatives were indeed formed. The absence of this peculiar behavior in some other derivatives is consistent with smooth variations of acid‐base properties from one derivative to the next. The electrocatalytic properties of all the compounds are illustrated by the reduction of nitrite by reduced PW18 and of nitrate by reduced α2‐PW17Cu. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Tuning the Magnetic Properties of a Dinuclear Copper Complex: From Ferromagnetic to Antiferromagnetic Coupling
Authors: Foxon Simon P. , Walter Olaf , Koch Robert , Rupp Holger , Müller Paul , Schindler Siegfried 
Published: January 2004

AbstractA novel structural motif in oxalate bridged copper(II) complexes has been prepared namely a metallamacrocyclic compound of the dinucleating ligand 1,3‐bis[bis(2‐pyridylmethyl)amino]benzene (= 1,3‐tpbd). It could be demonstrated that the magnetic properties of copper(II) complexes of the 1,3‐tpbd ligand can be adjusted from weakly ferromagnetic (J = +9.3 cm−1) to strongly antiferromagnetic [J = −366(9) cm−1] by variation of the additional ligands (e.g. perchlorate, azide, oxalate etc.). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Synthesis, Spectroscopic Properties, and Structure of [Tetrakis(2,4‐dimethyl‐3‐pentyloxy)phthalocyaninato]metal Complexes
Authors: Liu Wei , Lee Chi‐Hang , Chan Hoi‐Shan , Mak Thomas C. W. , Ng Dennis K. P. 
Published: January 2004

AbstractA series of highly soluble [tetrakis(2,4‐dimethyl‐3‐pentyloxy)phthalocyaninato]metal complexes [MPc(OC7H15)4] (M = Zn, Pd, Co) were prepared by cyclic tetramerization of 3‐(2,4‐dimethyl‐3‐pentyloxy)phthalonitrile (2) in the presence of the corresponding metal salts and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in n‐pentanol. For M = Zn and Pd, two major isomers with a C4h and C2v symmetry were isolated by column chromatography and characterized with various spectroscopic methods, while the cobalt analogue showed only the C4h isomer. The (phthalocyaninato)manganese complex [MnClPc(OC7H15)4] was also synthesized by metallation of the metal‐free phthalocyanine H2Pc(OC7H15)4 formed by treating 2 with CeCl3 and DBU in n‐pentanol. The structures of the C4h isomers of the (phthalocyaninato)zinc and ‐cobalt complexes and the C4 isomer of the manganese analogue were also established by X‐ray diffraction analyses. The palladium counterpart formed a novel 1:1 inclusion complex with oxalic acid, the crystal structure of which was also determined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)