Stereochemistry of heterobinuclear Pt-M complexes

2017 ◽  
Vol 37 (3-4) ◽  
pp. 131-146 ◽  
Author(s):  
Milan Melnik ◽  
Peter Mikus
Keyword(s):  
Structural Parameters ◽  
The Other ◽  
Oxidation States ◽  
Central Metal ◽  
Metal Atoms ◽  
Square Planar ◽  
Coordination Spheres

AbstractIn this review, the structural parameters of almost 30 isomers of heterobinuclear Pt-M (M=Sn, Tl, Cu, Ag, Ti, W, Cr, Fe, Co, Ni, Mn, Pd, or Rh) complexes are summarized and analyzed. There are three types of isomers: distortion (by far the prevailing type), polymerization, and mixed isomers. On the basis of Pt-M distance, there are two groups of complexes: one in which the Pt-M bond distances are <3.0 Å (M=Sn, Tl, W, Cr, Mn, Ni, or Pd) and the other one in which the Pt-M separations are >3.0 Å (M=Cu, Ag, Ti, W, Fe, Co, or Rh). Platinum atoms exist in two oxidation states: +2 and +4. The former by far prevails with a square-planar arrangement with varying degrees of distortion. The Pt(IV) atoms are six-coordinated. The inner coordination spheres about M atoms range from two-coordinated (AgNCl) to sandwiched (FeC10). There is wide variety of donor atoms (ligands) (H, OL, NL, CL, BL, Cl, SL, PL, Br, or I) that build up the respective inner coordination spheres about central metal atoms.

scholarly journals Mixed Ligand Complexes of Copper(II) and Cobalt(II) with Hydrazones Derivatives and ortho-Vanillin: Syntheses, Characterizations and Antimicrobial Activity

2019 ◽  
Vol 35 (6) ◽  
pp. 1722-1730
Author(s):  
Israa A. Alghamdi ◽  
Mohamed Abdelbaset ◽  
Ines El Mannoubi
Keyword(s):  
Metal Complexes ◽  
Antimicrobial Activities ◽  
Molar Conductance ◽  
Mixed Ligand ◽  
Planar Geometry ◽  
Central Metal ◽  
Bacterial Strains ◽  
Hydrazone Ligand ◽  
Metal Atoms ◽  
Square Planar

The purpose of this paper was to synthesis new mixed-ligand Cu(II) and Co(II) metal complexes utilizing bidentate and tridentate donor hydrazones derivatives as primary ligands and o-vanillin as co-ligand. The obtained compounds were characterized by elemental analysis, Infrared, UV-Vis., 1H-NMR, Mass spectra, molar conductance, thermal analysis and atomic absorption spectroscopy (ASS). Spectroscopic analysis results indicated that the hydrazone ligand (L1) behave as tridentate (ONO) and forms metal complexes having distorted square planar geometry. While the ligands (L2, L3 AND L4) behave as bidentate (NO) and forms metal complexes having octahedral geometry around the central metal atoms. The antimicrobial potentials were assessed for the ligand (L2) and its metal complexes only and were screened against six types of bacterial strains and one fungal strain. The antimicrobial activities results of the tested compounds showed enhanced activity of the complexes over their parent ligands.

Cyano-bridged heterodinuclear complexes of nickel(II) and palladium(II). A disordered structure for the linkage isomer [LPd-CN-NiL](ClO4)

1992 ◽  
Vol 70 (9) ◽  
pp. 2461-2467 ◽  
Author(s):  
Parimal Paul ◽  
Ramprasad Das ◽  
Kamalaksha Nag ◽  
Eric J. Gabe ◽  
Jean-Pierre Charland
Keyword(s):  
Direct Methods ◽  
The Other ◽  
Tridentate Ligand ◽  
Full Matrix ◽  
X Ray ◽  
Disordered Structure ◽  
Metal Atoms ◽  
Square Planar ◽  
C And N ◽  
Cyanide Bridge

The homodinuclear [M2L2μ(CN)](ClO4) complexes and the heterodinuclear [LPd-CN-NiL](ClO4) and [LNi-CN-PdL](ClO4) complexes of nickel(II) and palladium(II) have been synthesized with a tridentate ligand HL (methyl 2-[(2′-aminoethyl)amino]cyclopent-1-enedithiocarboxylate). In solution both the isomers dissociate, [LNi-CN-PdL]+ much more rapidly than [LPd-CN-NiL]+, and a steady state equilibrium between the [LPd-CN-NiL]+, [Pd2L2μ-(CN)]+, and [Ni2L2μ-(CN)]+ species is established. The isomer [LPd-CN-NiL]+ exhibits a band at 555 nm that is absent in the other isomer and homodinuclear complexes. The X-ray structure of [LPd-CN-NiL](ClO4) has been studied. Crystals of the compound are monoclinic, a = 8.964(2), b = 23.852(2), c = 14.096(2) Å, β = 105.92(1)°, Z = 4, space group P21/a. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.054 and Rw = 0.034 for 4426 reflections with I ≥ 2.5σ(I). The two metal centres are in a square-planar environment provided by the N2S donor set of the ligand and cyanide bridge, but the metal atoms as well as C and N atoms of μ-CN could not be distinguished due to disorder. An alternate stacking of Pd-CN-Ni and Ni-NC-Pd units has been proposed to explain the 1:1 occupancy of the atoms concerned.

scholarly journals Crystal structures of a copper(II) and the isotypic nickel(II) and palladium(II) complexes of the ligand (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-ol

2016 ◽  
Vol 72 (8) ◽  
pp. 1093-1098 ◽  
Author(s):  
Souheyla Chetioui ◽  
Djamil-Azzeddine Rouag ◽  
Jean-Pierre Djukic ◽  
Christian G. Bochet ◽  
Rachid Touzani ◽  
...  
Keyword(s):  
Complex I ◽  
Ring System ◽  
Naphthalene Ring ◽  
Acta Cryst ◽  
Π Interactions ◽  
Metal Atoms ◽  
Square Planar ◽  
Coordination Spheres ◽  
Solvent Molecules ◽  
Planar Geometries

In the copper(II) complex, bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}copper(II), [Cu(C16H8Br3N2O)2], (I), the metal cation is coordinated by two N atoms and two O atoms from two bidentate (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olate ligands, forming a slightly distorted square-planar environment. In one of the ligands, the tribromobenzene ring is inclined to the naphthalene ring system by 37.4 (5)°, creating a weak intramolecular Cu...Br interaction [3.134 (2) Å], while in the other ligand, the tribromobenzene ring is inclined to the naphthalene ring system by 72.1 (6)°. In the isotypic nickel(II) and palladium(II) complexes, namely bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}nickel(II), [Ni(C16H8Br3N2O)2], (II), and bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}palladium(II), [Pd(C16H8Br3N2O)2], (III), respectively, the metal atoms are located on centres of inversion, hence the metal coordination spheres have perfect square-planar geometries. The tribromobenzene rings are inclined to the naphthalene ring systems by 80.79 (18)° in (II) and by 80.8 (3)° in (III). In the crystal of (I), molecules are linked by C—H...Br hydrogen bonds, forming chains along [010]. The chains are linked by C—H...π interactions, forming sheets parallel to (011). In the crystals of (II) and (III), molecules are linked by C—H...π interactions, forming slabs parallel to (10-1). For the copper(II) complex (I), a region of disordered electron density was corrected for using the SQUEEZE routine inPLATON[Spek (2015).Acta Cryst.C71, 9–18]. The formula mass and unit-cell characteristics of the disordered solvent molecules were not taken into account during refinement.

Platinum organometallic compounds: classification and analysis of crystallographic and structural data of monomeric five and higher coordinated

2013 ◽  
Vol 33 (1) ◽  
pp. 13-103 ◽  
Author(s):  
Milan Melník ◽  
Peter Mikuš ◽  
Clive Eduard Holloway
Keyword(s):  
Organometallic Compounds ◽  
Structural Data ◽  
Oxidation States ◽  
Trans Effect ◽  
Trigonal Bipyramidal ◽  
Square Planar ◽  
Coordination Spheres ◽  
Organoplatinum Compounds

AbstractFour hundred and twenty monomeric organoplatinum compounds, in which platinum atoms are five- and higher coordinated, are analyzed. The platinum atoms are found in the oxidation states +2, +3 and +4. The Pt(II) compounds by far prevail. There are wide varieties of the inner coordination spheres about the platinum centers. The Pt(II) compounds are five-coordinated (trigonal bipyramidal and square pyramidal), six-coordinated (different degrees of distortion), seven-coordinated (pentagonal bipyramidal, piano stool) and sandwiched (PtC10). The Pt(III) compound is square-planar. The Pt(IV) compounds are six- and eight-coordinated. There are several relationships between the Pt-L bond distances, covalent radii of the coordinated atom/ligand, and metallocycles, which are discussed. The trans-effect plays an important role in the inner coordination spheres about the Pt centers, especially on the Pt-L bond distances.

Analysis of crystallographic and structural data of polymeric iron-alkaline metal complexes

2011 ◽  
Vol 34 (5-6) ◽  
pp. 93-126
Author(s):  
Milan Melnik ◽  
Markku Rafael Sundberg ◽  
Rolf Uggla
Keyword(s):  
Coordination Number ◽  
Iron Atom ◽  
Structural Parameters ◽  
Structural Data ◽  
Oxidation States ◽  
Alkaline Metal ◽  
Coordination Numbers ◽  
Metal Atoms ◽  
Polymeric Chains ◽  
Group 1

Abstract The present review covers almost 100 polymeric MFe (M=Li, Na, K, Rb, and Cs) compounds. The metal atoms of group 1 as partners with iron atom build up complex polymeric chains. The iron atoms are found in the oxidation states 0, +2, and +3, of which the oxidation state +3 prevails. The coordination number of the iron atom ranges from 2 to 10 (sandwiched). The coordination sphere about the main group 1 metals varies, ranging from tetrahedral to mostly trigonal bipyramid. There are also higher coordination numbers involved, namely, from 6 to 10. The most common ligand atoms are oxygen and nitrogen. There are three compounds displaying distortion isomerism. Several relationships between structural parameters are found and discussed.

Structural aspects of heterotrinuclear Pt2M, PtM2, and PtMM′ complexes – distortion isomers

2018 ◽  
Vol 38 (4) ◽  
pp. 151-162 ◽  
Author(s):  
Milan Melnik ◽  
Peter Mikus ◽  
Andrea Forgacsova ◽  
Maria Bodnar Mikulova
Keyword(s):  
Structural Parameters ◽  
Bond Angles ◽  
Metal Atoms ◽  
Metal Metal ◽  
Coordination Spheres ◽  
Independent Molecules ◽  
Structural Aspects ◽  
Metal Ligand ◽  
Ligand Bond

AbstractIn this review, the structural parameters of 18 heterotrinuclear Pt2M (M=Hg, Zn, Cd, Au, Mn, Ag, Pd), PtM2 (M=Al, Ga, Sb, In, Mo, Fe), PtFeMn, PtHgMn, and PtFeOs types are summarized and analyzed. The Pt atoms are four-, five-, and even six-coordinated, among which the four-coordinated ones are the most common. The M atoms are found to be two- (Hg), three- (Hg), four- (Hg, Sb, In, Ag, Au), and six- (Ga, In, Al, Mo, Mn, Fe, Pd) coordinated and even sandwiched (FeC10). There is a wide variety of donor atoms (ligands) (O+NL, N+CL, NL, CO, CN, CL, Cl, SL, PL, I), which build up the respective inner coordination spheres about the metal atoms. The 17 complexes contain two crystallographically independent molecules within the same crystal, and 1 complex contains four such molecules. In each complex, the respective molecules are differing mostly by the degree of distortion in metal-metal and metal-ligand bond distances and ligand-metal-ligand bond angles, and are examples of distortion isomerism.

Synthesis and Characterization of New Zinc Phthalocyanine - Dodecenyl Succinic Anhydride Benzoic Groups

2020 ◽  
Vol 17 (6) ◽  
pp. 488-495
Author(s):  
Hussein Ali Al-Bahrani ◽  
Mohanad Mousa Kareem ◽  
Abdul Amir Kadhum ◽  
Nour A. Alrazzak
Keyword(s):  
Salicylic Acid ◽  
Succinic Anhydride ◽  
Zinc Phthalocyanine ◽  
Central Metal ◽  
Target Compound ◽  
Compound I ◽  
Metal Phthalocyanines ◽  
Metal Atoms ◽  
Amino Salicylic Acid

Background: The phthalocyanines a series of compounds involves four iso-indole units linked by aza nitrogen atoms bonded with metal atoms that are normally located in the center a phthalocyanines ring. Some of the central metal-phthalocyanines can be excited by ultraviolet light and emit a fluorescence in far-red region. Objective: To synthesize a derivative of phthalocyanines namely 4,4',4' '-tri-(dodecenyl succinic anhydride)- 4' ' '-(5-amino salicylic acid) zinc phthalocyanine with a zinc central metal. Materials and Methods: The reaction of 4- nitro Phthalonitrile and 4- amino Phthalonitrile with ZnCl2 in the presence of dimethyl amino ethanol afforded 4,4',4' '-triamino-4' ' '-nitro zinc phthalocyanine. This product reacted with 5-amino salicylic acid to yield tetra-(5-amino salicylic acid) zinc phthalocyanine. A dodecenyl succinic anhydride was added on the amine group of benzoic rings to afford 4,4',4' '-tri-(dodecenyl succinic anhydride)-4' ' '-(5-amino salicylic acid) zinc phthalocyanine(I), the target compound. Results and Discussion: Compound I is successfully synthesized with a yield of 72% from tetra-(5-amino salicylic acid) zinc phthalocyanine with dodecenyl succinic anhydride. Conclusion: The newly synthesized molecule of 4,4',4' '-tri-(dodecenyl succinic anhydride)-4' ' '-(5-amino salicylic acid) zinc phthalocyanine (I), tetra-(5-amino salicylic acid) zinc phthalocyanine(E) and 4,4',4' '- triamino-4' ' '-nitro zinc phthalocyanine (S). The reaction of 4- nitro Phthalonitrile and 4- amino and the structure of compound I is confirmed and its formation was proven.

scholarly journals Influence of Physicochemical Properties and Parent Material on Chromium Fractionation in Soils

Processes ◽  
2021 ◽  
Vol 9 (6) ◽  
pp. 1073
Author(s):  
Claudia Campillo-Cora ◽  
Laura Rodríguez-González ◽  
Manuel Arias-Estévez ◽  
David Fernández-Calviño ◽  
Diego Soto-Gómez
Keyword(s):  
Physicochemical Properties ◽  
Contaminated Soils ◽  
Research Work ◽  
Parent Material ◽  
The Other ◽  
Oxidation States ◽  
Diethylenetriaminepentaacetic Acid ◽  
Remediation Strategies ◽  
Exchangeable Aluminum ◽  
Efficient Extraction

Chromium is an element that possess several oxidation states and can easily pass from one to another, so its behavior in soils is very complex. For this reason, determining its fate in the environment can be difficult. In this research work we tried to determine which factors affect the chromium fractionation in natural soils, conditioning chromium mobility. We paid special attention to the parent material. For this purpose, extraction experiments were carried out on spiked soils incubated for 50–60 days, using H2O, CaCl2 and diethylenetriaminepentaacetic acid (DTPA). The most efficient extraction rate in all soils was achieved using water, followed by CaCl2 and DTPA. We obtained models with an adjusted R2 of 0.8097, 0.8471 and 0.7509 for the H2O Cr, CaCl2 Cr and DTPA Cr respectively. All models were influenced by the amount of chromium added and the parent material: amphibolite and granite influenced the amount of H2O Cr extracted, and schist affected the other two fractions (CaCl2 and DTPA). Soil texture also played an important role in the chromium extraction, as well as the amounts of exchangeable aluminum and magnesium, and the bioavailable phosphorus. We concluded that it is possible to make relatively accurate predictions of the behavior of the different Cr fractions studied, so that optimized remediation strategies for chromium-contaminated soils can be designed on the basis of a physicochemical soil characterization.

scholarly journals Hydrothermal Crystallization of Bismuth Oxychlorides (BiOCl) Using Different Shape Control Reagents

Materials ◽  
2021 ◽  
Vol 14 (9) ◽  
pp. 2261
Author(s):  
Enikő Bárdos ◽  
Viktória A. Márta ◽  
Szilvia Fodor ◽  
Endre-Zsolt Kedves ◽  
Klara Hernadi ◽  
...  
Keyword(s):  
Surface Tension ◽  
Shape Control ◽  
Cetyltrimethylammonium Bromide ◽  
Optical Band Gap ◽  
Structural Parameters ◽  
Band Gap Energy ◽  
Oxidation States ◽  
Cetyltrimethylammonium Chloride ◽  
Hydrothermal Crystallization ◽  
Sodium Dodecylsulphate

Bismuth oxychloride photocatalysts were obtained using solvothermal synthesis and different additives (CTAB—cetyltrimethylammonium bromide, CTAC—cetyltrimethylammonium chloride, PVP–polyvinylpyrrolidone, SDS–sodium dodecylsulphate, U—urea and TU—thiourea). The effect of the previously mentioned compounds was analyzed applying structural (primary crystallite size, crystal phase composition, etc.), morphological (particle geometry), optical (band gap energy) parameters, surface related properties (surface atoms’ oxidation states), and the resulted photocatalytic activity. A strong dependency was found between the surface tension of the synthesis solutions and the overall morpho-structural parameters. The main finding was that the characteristics of the semiconductors can be tuned by modifying the surface tension of the synthesis mixture. It was observed after the photocatalytic degradation, that the white semiconductor turned to grey. Furthermore, we attempted to explain the gray color of BiOCl catalysts after the photocatalytic decompositions by Raman and XPS studies.

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