eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
85
92
10.22036/icr.2016.46261
46261
Synthesis, Characterization and Theoretical Studies of a New Macroacyclic Schiff-Base Ligand Containing Piperazine Moiety and Related Mn(II), Cu(II), Ni(II) and Cd(II) Complexes
Majid Rezaeivala
mrezaeivala@gmail.com
1
Department of Chemical Engineering, Hamedan University of Technology, Hamedan, 65155, Iran
Four new [NiH2L](ClO4)2 (1), [CuH2L](ClO4)2 (2), [MnH2L](ClO4)2 (3) and [CdH2L](ClO4)2 (4), complexes were prepared by the reaction of a new Schiff base ligand and Cu(II), Ni(II), Mn (II) and Zn (II) metal ions in equemolar ratios. The ligand, H2L was synthesized by reaction of 1, 4- bis (2- formylphenyl) piperazine and ethanol amine and characterized with IR and 1H,13C NMR spectroscopy. All complexes were characterized by IR, Mass and elemental analysis. Also, theoretical studies on structures, molecular orbital and nature of bond in latter complexes were carried out with NBO analysis at DFT (BP86) method using Def -2/SVP basis set . The results of WBI and Charge transfer confirm that the covalent character in bonding interactions between the H2L and metal ions in latter complexes are as following: [MnH2L]2+[NiH2L]2+<[CdH2L] 2+<[CuH2L]2+. Also the calculated total spin density for Mn2+, Ni2+ and Cu2+ metal ions are about 4.76, 1.49, and 0.45, respectively.
https://www.inorgchemres.org/article_46261_d1d5296c013ea422dcf9a965f036e05f.pdf
Schiff base
Metal complexes
Piperazine
Ethanolamine
Theoretical study
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
93
104
10.22036/icr.2016.46355
46355
Plumbum(II) and Zinc(II) Complexes with 5-Chlorosalicylic Acid: Structure and Propertie
Kai-Fei Wu
437451408@qq.com
1
Yu Feng
849985614@qq.com
2
Fen Jiang
1184537676@qq.com
3
Xian-Li Bai
810357725@qq.com
4
Xian-Hong Yin
2386754631@qq.com
5
Guangxi University for Nationalities
Guangxi University for Nationalities
Guangxi University for Nationalities
Guangxi University for Nationalities
Guangxi University for Nationalities
Abstract: Two new transition metal complexes, containing the acidic ligand 5-chlorosalicylic acid (H2L5), and 1,10-phenanthroline(phen) and 1,3-Di(4-pyridyl)propane (bpp) as secondary ligands are reported. They are formulated as {[Pb(HL5)2(phen)(H2O)]·H2O}n(1), [Zn2(HL5)4(bpp)2]n(2). All the complexes are characterized by single-crystal X-ray diffractions. Compoud 1 crystallizes in the triclinic P-1 space group while compoud 2 in the monoclinic system with space group C2/c. In compund 1, the carboxylate group of the coordinated HL5- adopt μ1−η1: η0 coordination fashion to connect one Pb(II) ion but all the carboxylate groups adopt the different μ1−η1: η1 mode in the crystal of compoud 2 compared to 1. In addition, the carboxylate group and Hydroxyl can partly or entirely deprotonated, which makes it possible to coordinating with metal ion or forming hydrogen bonding interactons. Furthermore, the fluorescence property in the solid state and thermal decomposition process were investigated in order to understand the relationships between the structures and the properties.
https://www.inorgchemres.org/article_46355_e707fa0264dd5c2bee1321e0c9225a38.pdf
Transition metal complexes
Single-crystal X-ray diffractions
Solid-state photoluminescent properties
Thermal decomposition process
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
105
114
10.22036/icr.2017.27860.1025
46374
Synthesis and Crystal Structure of Cobalt(III) Complexes of Salen Type Schiff Bases and Tertiary Phosphanes as Ligands
Ali Hossein Kianfar
akianfar@cc.iut.ac.ir
1
Hamid Reza Khavasi
2
Department of Chemistry, Isfahan University of Technology, Isfahan, Iran, 84156-83111
Department of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
The new [Co(Salen)(PBu3)2]ClO4, [Co(Salen)(PBu3)2]BF4, [Co(Salpn)(PBu3)2]ClO4 and [Co(Salen)(PMe2Ph)2]ClO4 ( where salen = bis(salisylaldehyde)ethylenediimine)) complexes were synthesiszed and chracterized by IR, UV-Vis, 1H NMR spectroscopy and elemental analysis. The IR and 1H NMR spectra cofirmed that the synthesised complexes contain Schiff base ligand, phosphane and conter ion and the elemental analysis is in good agreement with those calculated for the proposed formula. The coordination geometry of [Co(Salen)(PMe2Ph)2]ClO4 and [Co(Salen)(PBu3)2]ClO4 complexes were determined by X-ray crystallography. It has been found that all the complexes are hexa coordinate in the solid state. Cobalt atom exhibits a distorted octahedral geometry and the salen ligand has the N2O2 coordinated environment in the equatorial plane. Cobalt complexes with ligands derived from salicylaldehyde have been well studied.[1] They are regarded as models for the Cobalamine (B12) coenzymes [2-4] classified as an oxygen carrier [5] and used as a catalyst for the preparative oxygenation of phenols [6] indols [7] and amines.[8]. The catalytic activity of Co(III) with salen complexes has been investigated. It was shown the catalytically active species contains cobalt in the Co(III) oxidation state [9-15].
https://www.inorgchemres.org/article_46374_6cb628ee3186ba50efce537f573e6d21.pdf
Schiff base
Phosphane
Cobalt(III) complexes
X-Ray crystal structure
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
115
122
10.22036/icr.2017.43519.1028
46376
Synthesis and Characterization of Binuclear Zn(II) Complex of N2O2S Symmetrical Potentially Pentadentate Schiff Base Ligand
Ahmad Ali Dehghani-Firouzabadi
aadehghani@yazd.ac.ir
1
Tahereh Alizadeh
ta.al1366@gmail.com
2
Department of Chemistry, Faculty of Science, Yazd University, 89195-741 Yazd, Iran
Department of Chemistry, Faculty of Science, Yazd University, 89195-741 Yazd, Iran
The reactions of 1 - chloro - 2 - nitro benzene with 2 - Amino thio phenol yield the 2 - ( ( nitro phenyl ) thio ) aniline and then 2 , 2' - thio dianiline of this compound was prepared . Also the symmetrical potentially pentadentate N 2 O 2 S Schiff base ligand 2 , 2' - ( ( ( thio bis (1 , 2 - phenylene ) ) bis ( azanilidene ) ) bis ( methenilidene ) ) diphenol ( H 2 L ) obtain by added salicylaldehyde . These compound have been characterized by FT - IR , 1 H NMR and Mass Spectrometry . Bi - nuclear Zn ( II ) complex of this ligand was prepared and structurally characterized by X - ray crystallography . The coordination geometry around Zn ( II ) is intermediate between trigonal bipyramidal and square pyramidal , τ = 0.54.
https://www.inorgchemres.org/article_46376_670f577c7e9759d8b2d5448af7bd62d6.pdf
Schiff base complex
Pentadentate ligand
Zn(II) complex
Binuclear complex
N2O2S donor
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
123
130
10.22036/icr.2017.46790.1030
46377
Investigation of Catalytic Activity of Bis[2-(p-tolyliminomethyl)phenolato] Copper(II) Complex in the Selective Oxidation of Alcohols with Hydrogen Peroxide
Mehdi Hatefi Ardakani
m_hatefi_chem@yahoo.com
1
Samira Saeednia
s.saeednia@vru.ac.ir
2
Marziyeh Mohammadi
m.mohammadi@vru.ac.ir
3
Esmaeil Mandegari-Kohan
m92371004@post.vru.ac.ir
4
Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan, 77188-97111, Rafsanjan, Iran
Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan, 77188-97111, Rafsanjan, Iran
Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan, 77188-97111, Rafsanjan, Iran
Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan, 77188-97111, Rafsanjan, Iran
In this article, the catalytic activity of bis[2-(p-tolyliminomethyl)phenolato] copper(II) complex was studied, for the first time, in the oxidation of various primary and secondary alcohols to the corresponding aldehydes or ketones. The effect of different solvent was studied in the oxidation of benzyl alcohol and methanol was chosen as the reaction medium. Also the effect of different oxidants such as H2O2, urea-H2O2 (UHP), NaOCl, tert- BuOOH (TBHP) and NaIO4 was studied in the oxidation of benzyl alcohol and H2O2 was selected as oxygen donor. In this catalytic system, oxidation of benzyl alcohol required 4 mol% of catalyst for completion and with increasing the reaction temperature to 60 °C, the highest oxidation yield was observed. Results showed that this homogeneous catalyst, exhibited good catalytic activity in the selective oxidation of various alcohols with hydrogen peroxide and gave the corresponding aldehyde without further oxidation to carboxylic acids in good to excellent yields (56-95%).
https://www.inorgchemres.org/article_46377_03b6434c6b1c7ea448b7fd7284f299d5.pdf
Schiff base
Copper(II) complex
Homogeneous catalyst
alcohol
oxidation
Hydrogen peroxide
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
131
140
10.22036/icr.2017.24252.1022
46379
Natural Bond Orbital (NBO) Study of (5H-tetrazol-1-yl)(triphenylphosphine)gold [Au(tetz)(PPh3)]
Mehdi Nabati
mnabati@ymail.com
1
Mehrdad Mahkam
memahkam@yahoo.com
2
Chemistry Department, Faculty of Science, Azarbaijan Shahid Madani University, Tabriz, Iran
Chemistry Department, Faculty of Science, Azarbaijan Shahid Madani University, Tabriz, Iran
In this research work, we studied theoretically the structural properties of (5H-tetrazol-1-yl)(triphenylphosphine)gold or [Au(tetz)(PPh3)] by density functional theory (DFT) method at LANL2DZ level. All calculations were performed at 298.15 K and 1 atmosphere. Firstly, the bond lengths, bond angles, dihedral angles and natural charge density on atoms of the compound were calculated. The dependence between the experimental and calculated indicates a great convergence. The results have provided that the molecular structure of the compound is linear environment around gold atom. According to the calculations, the total natural charge of gold atom is consistent with the total number of electrons in the isolated gold atom. Natural bond orbitals (NBOs) analysis was then calculated at studied level of B3LYP (Becke, 3 parameter, Lee-Yang-Parr) theory. The NBO analysis revealed that the largest negative and positive charges are located on nitrogen (that coordinating to the gold) and phosphorus atoms, respectively.And also, it showed that the phosphorus atom uses more p orbital for formation of σ(Au-P) bond to formation of σ(P-C) bond.
https://www.inorgchemres.org/article_46379_ca52a22cc6f683a905c58601c425299a.pdf
Density functional theory
Natural bond orbital
Natural charge
Theoretical study
Gold(I) complexes
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
141
151
10.22036/icr.2017.27926.1026
46809
The Flight of the Monarch: [Cu(L)(CH3CN)(PPh3)]ClO4 (L = 2,5-Diphenyl-3,4-bis(2-pyridyl) Cyclopenta-2,4-dien-1-one)
Ahmad Amiri
ahmadamiri@ut.ac.ir
1
Mohammad Reza Binaeizadeh
2
Farzaneh Fadaei
fadaei23@gmail.com
3
Kurt Schenk-Joß
kurt.schenk@epfl.ch
4
Department of Chemistry, College of Science, University of Tehran, Tehran 14155-6455, Iran
Department of Chemistry, College of Science, University of Tehran, Tehran 14155-6455, Iran
CCC-IPSB, École Polytechnique Fédérale de Lausanne, Le Cubotron, Dorigny, CH-1015 Lausanne, Switzerland
CCC-IPSB, École Polytechnique Fédérale de Lausanne, Le Cubotron, Dorigny, CH-1015 Lausanne, Switzerland
The mononuclear complex [Cu(L)(CH3CN)(PPh3)]ClO4, (1), (L= 2,5-diphenyl-3,4-bis(2-pyridyl)cyclopenta-2,4-dien-1-one), has been synthesized and investigated by elemental analysis, IR, 1H NMR, UV-Vis spectroscopic methods and X-ray diffraction. The complex crystallizes in the non-centrosymmetric space group P212121 in accord with the asymmetric (atropisomer) Cu centre. Its coordination polyhedron has four vertices and is devoid of any symmetry. The [Cu(L)(CH3CN)(PPh3)]ClO4 is amongst the few MeL complexes crystallizing in a non-centrosymmetric space group. The bite-angle of the bidentate ligand L is 90.92(13)°, indicating some strain in the structure; this entails an enhanced instability of the complex with respect to strongly coordinating solvents. The crystal of 1 owes its cohesion to a multitude of weak C-H...O and C-H... interations. The electrochemistry of the complex shows three reversible ligand-centred reduction processes and an irreversible metal-centred one. This indicates that the coordination of the CuI(CH3CN)(PPh3) moiety to the L leads to the delocalization of electron density from L to the CuI(CH3CN)(PPh3) moiety.
https://www.inorgchemres.org/article_46809_d427f8e32ff6101649416d0da7089b57.pdf
Cu(I) complexes
Diene
crystal structure
Electrochemistry
Electrocatalyst
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
152
161
10.22036/icr.2017.69189.1034
54462
The Kinetic and Thermal Degradation Studies of N-(4-Acetyl-phenyl)-acetimidic Acid Pyridine-3-yl ester Metal(II) Complexes
Shraddha Shukla
shuklashraddha25@gmail.com
1
A.P. Mishra
apm19@rediffmail.com
2
Dept of chemistry
Dr H S Gour University Sagar
Dept of Chemistry Dr H S Gour University Sagar
Schiff base complexes of transition metals are of particular interest to inorganic chemists because of their structural, spectral and chemical properties, which are often strongly dependant on the nature of the ligand structure. Large number of metal (II) complexes with Schiff-base ligands has been extensively studied for their interesting structural specialties, applications and properties. The coordination complexes of [Co(C15H15N2O2)2(H2O)2]. Cl2.2H2O and [Cu(C15H15N2O2)2(H2O)2].Cl2 with the Schiff base N-(4-Acetyl-phenyl)-acetimidic acid pyridine-3-yl ester derived from 4-aminoacetophenone with 3-acetoxypyridine have been synthesized and characterized by micro analytical data; FT-ir, UV-vis, FAB- mass and thermal analysis studies. Thermal data show degradation of complexes. We carried out thermal analysis at 10 . The activation thermodynamic parameters, such as activation energy (E*), entropy of activation (DS*), enthalpy of activation (DH*) and Gibbs free energy (DG*) have been calculated with the help of TG, DTA and DTG curves using Coats–Redfern (C-R) method. The stoichiometry of the complexes are in 1:2 (M:L) molar ratio. Synthesized complex has been tested for their reactivity and substitution behavior.
https://www.inorgchemres.org/article_54462_9dfd4ae8fc1634a6aaeb230c742742a1.pdf
Thermal analyses
4-Aminoacetophenone
3-Acetoxypyridine and N-(4-acetyl-phenyl)-acetimidic acid pyridine-3-yl ester complex
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
162
170
10.22036/icr.2017.56994.1033
54461
Mild and Efficient Oxidation of Alcohols with NaIO4 Catalyzed by a Manganese Porphyrin-polyoxometalate Hybrid Material
Mehdi Araghi
mehdi.araghi83@yahoo.com
1
Department of Chemistry, Saveh Branch, Islamic Azad University, Saveh, Iran
Efficient and selective oxidation of alcohols with NaIO4 catalyzed by an organic-inorganic hybrid material in which manganese(III)5,10,15,20-tetrakis(4-aminophenyl)porphyrin chloride, MnIII(TAPP)Cl, is covalently linked to a Lindqvist structure of polyoxometalate, Mo6O192-, at room temperature is reported. The effect of various parameters such as catalyst amount, solvent and oxidant were studied. The catalyst, MnP-POM, showed high activity not only in the oxidation of benzylic and linear alcohols but also in the oxidation of secondary alcohols and their corresponding ketones were obtained in good yields. A good selectivity observed in the case of cinnamyl alcohol and the only alcoholic group is oxidized and no epoxide was obtained. The MnP-POM catalyst is stable under the reaction conditions and While, the homogeneous MnIII(TAPP)Cl cannot recover even one time, the hybrid catalyst can be filtered and reused several times without significant loss of its initial activity. Covalent linkage of the MnIII(TAPP)Cl to the POM provide way of stabilizing the metalloporphyrin against deactivation during the catalytic cycles
https://www.inorgchemres.org/article_54461_94bc2982cdc507a2d84a26160ab2ef22.pdf
Polyoxometalate
Porphyrin
Hybrid material
oxidation
Heterogeneous catalyst
Alcohols
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
171
182
10.22036/icr.2017.75164.1035
54463
Sonochemical Synthesis of Novel Nano Flower Lead(II) Metal-organic Coordination Polymer: A New Precursor to Produce Nano-sized PbO
Babak Mirtamizdoust
babakm.tamizdoust@gmail.com
1
Reza Safari
safari_physicalchemistry@yahoo.com
2
Saeed Anbarteh
sanbarteh@gmail.com
3
Inorganic chemistry
Qom univ./physical chemistry
Inorganic chemistry
Metal-organic coordination polymers are a class of organic–inorganic materials consists of metal ions linked together through multi-dentate organic ligands, to form a polymeric chain. These materials have received a great deal of attention in a wide range of different areassuch as catalysis, sensing, luminescence, separation and storage used . The new nano flowerPb(II) 1Dmetal-organic chain {[Pb(phen)(μ-CH3COO)]•(BF4)}n(1) (phen=1,10-phenanthroline) was synthesized by a sonochemical irradiation assisted method. The compound was characterized by scanning electron microscopy (SEM), elemental analysis, FT-IR spectroscopy, X-ray powder diffraction (XRPD) and single crystal X-ray analysis. The X-ray analysis reveals a 1Dchain metal-organic coordination polymer structure for 1 thatis further extended into a 3D supramolecular structure by π-π and other labile interactions. The coordination number of the lead(II) ions is determined was abouteight, PbF2N2O4. The lead oxide nanoparticles were prepared at 180 °C by the thermolysis of 1. The average diameter of the nanoparticles to be 27 nm. The size and morphology of the prepared PbO samples were further observed using SEM.
https://www.inorgchemres.org/article_54463_6032c71a7025bd389789a02c8477dca6.pdf
Nanometal-organiccoordination polymer
Ultrasonicirradiation
1Dchain
Nano PbO
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
183
190
10.22036/icr.2017.93979.1038
54464
On the Polymorphism of 12-Tungstoborate Heteropolyanion: Structure Determination and Its Functionalization with L-proline
Mina Arefian
arena2493@yahoo.com
1
Masoud Mirzaei
mirzaeesh@um.ac.ir
2
Hossein Eshtiagh-Hosseini
heshtiagh@um.ac.ir
3
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad, Iran
Department of Chemistry,
Faculty of Science,
Ferdowsi University of Mashhad،
Mashhad، Iran
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad, Iran
A new structure related to previously reported structure of 12-tungstoborate Keggin-type polyoxometalate, K5[BW12O40], was synthesized and its characterization by single crystal X-ray diffraction shows the polymorph structure. Further attempts have been performed to provide three component compounds based on L-proline, lanthanoid cation and K5[BW12O40] (BW12 (II)) under hydrothermal conditions which is rarely reported in hybrid materials rather than other Keggin types. The proposed general structures contain lanthanoid dimers with amino acid bridges and BW12 (II), which characterized by elemental analysis, FT-IR spectroscopy and ICP (Inductively coupled plasma) method. Various types of interactions are established, depending on the POM shape and charge, the amino acid side chain, peptide sequence or protein structure. Experimental conditions such as temperature, acidity, solvent, etc. are also important factors that influence the binding/reactivity of POM with biomolecules, as described recently [13]. This understanding allows the adequate design of the POM-biomolecule couple for tailoring and controlling mechanisms of action such as catalysis, inhibition, and aggregation, or the crystallizing agent.
https://www.inorgchemres.org/article_54464_da7719b62d155241d52963921920bd09.pdf
12-Tungstoborate
L-proline
Polymorphism
Inorganic-organic hybrid
Hydrothermal reaction
eng
Iranian Chemical Society
Inorganic Chemistry Research
2538-1865
2018-12-01
2
1
191
201
10.22036/icr.2017.56071.1032
56965
Solvatochromic Properties of Heteroleptic Copper(II) Complexes Containing N,N,N',N'-Tetramethylethylenediamine and 2-Aacetylcyclopentanone Ligands
Hamid Golchoubian
h.golchobian@umz.ac.ir
1
Shahrbanoo Arabahmadi
sh_ahmadi684@yahoo.com
2
Department of Chemistry, University of Mazandaran, P. O. Box: 47416-95447, Babol-sar, Iran
Department of Chemistry, University of Mazandaran, P. O. Box: 47416-95447, Babol-sar, Iran
Three new heteroleptic copper(II) complexes, [(tmen)Cu(dike)H2O]X where tmen = N,N,N',N'-tetramethylethylenediamine, dike = 2-acetylcyclopentanone anion and X= ClO4- (1), Cl- (2) and Br- (3) are prepared and characterized by elemental analyses, molar conductance measurements and IR and UV-Vis spectroscopy techniques. The complex 1 is fairly soluble in various organic solvents and demonstrates distinctive solvatochromism. However, the solubility of complexes 2 and 3 is less than 1 and their color changes are limited to polar solvents. The influence of the solvent polarity and counter ions on the wave length maxima, max values of the d-d bands of the complexes have been investigated by visible spectroscopy. A multi-parametric equation has been utilized to explain the solvent effect on the d-d transition of [(tmen)Cu(dike H2O)]ClO4 using SPSS/PC software. The stepwise multiple linear regression (SMLR) method demonstrated that the donor power of the solvent plays the most important role in the observed negative solvatochromism of the compound.
https://www.inorgchemres.org/article_56965_900bcf63f0825016a652a92379e1fe26.pdf
Heteroleptic
Diketonate
Ethylendiamine
Copper(II)
Solvatochromism