Synthesis, Structure, Magnetic and Catalytic Competency of a
Tetradentate (NNOO) Schiff Base Mediated Dimeric Copper(II) Complex

One dinuclear copper(II) complex {μ-[2,2′-{ethane-1,2-diylbis[(azanylylidene)methanylylidene]}- bis(phenolato)]}-{μ-[2,2′-{ethane-1,2-diylbis[(azanylylidene)methanylylidene]}bis(phenolato)]}- dicopper(II), [Cu2(salen)2] (1) [salen2− = [2,2′-{ethane-1,2-diylbis[(azanylylidene)methanylylidene]}- bis(phenolato)] has been isolated and characterized by X-ray diffraction analysis and spectroscopic studies. X-ray single crystal structure examination revealed that each Cu(II) center in the asymmetric unit of 1 adopts a distorted square planar geometry with a CuN2O2 chromophore, where two asymmetric units are attached through congregation of Salen involving Cu-O bond to form dinuclear molecular unit [Cu2(salen)2]. In crystalline state, these dinuclear entities in 1 are extended through C-H···π interactions and π···π interactions displaying a 3D network structure. The variable-temperature magnetic susceptibility measurement asserted a dominant antiferromagnetic interaction between the copper(II) centers through Cu-O-Cu linkage in 1 with J = -1.46 cm-1. The catalytic efficacy of complex 1 was studied in a series of solvents for the oxidation of styrene and cyclooctene using tert-butyl-hydroperoxide (TBHP) as an active oxidant under mild conditions. The catalytic reaction mixture has been analyzed by gas chromatography and it displayed that the yield of the epoxidation and its selectivity is optimum in acetonitrile medium.

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Metal Complexes of π-Expanded Ligand (7): Syntheses, Structures and Properties of Pt(II) Complexes Containing the Isomeric 1- and 2-Alkyliminomethyl Pyrene Ligands

Crystals ◽

10.3390/cryst10060476 ◽

2020 ◽

Vol 10 (6) ◽

pp. 476 ◽

Cited By ~ 1

Author(s):

Xuan-Dien Luong ◽

Xuan-Truong Nguyen

Keyword(s):

Molecular Structure ◽

Planar Geometry ◽

X Ray Diffraction ◽

X Ray ◽

Pt Complex ◽

Physico Chemical ◽

Clear Explanation ◽

Square Planar ◽

Structures And Properties ◽

The Relationship

A [O,N] bidentate π-expanded ligand system, (E)-1-(n-octylimino)methylpyren-2-ol (2), was newly synthesized via a six-step synthesis from pyrene. The ligand 2 reacts with [PtCl2(PhCN)2] in chlorobenzene and the presence of a base at reflux for 2 h under the formation of (2(Pt)) complex with a yield of 70%. The molecular structure of (2(Pt)), studied by common spectroscopic methods and X-ray diffraction, shows a square planar geometry with a trans-configuration of the ligands. The molecular structure, absorption spectra, electrochemical properties, and phosphorescence characteristics of the (2(Pt)) complex are discussed, emphasizing the comparison with those of the previously reported Pt complex (1(Pt)) containing the isomeric ligands of 2, (E)-2-(n-octylimino)methylpyren-1-ol. The DFT calculations of the two Pt complexes are carried out and exhibit a clear explanation of the relationship between their physico-chemical characteristics.

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Darstellung von 1,3,5-Trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinanen; Einkristall-Röntgenstrukturanalyse eines Platin(II)-Komplexes/Preparation of 1,3,5-Trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinanes; Single Crystal X-Ray Diffraction Study of a Platinum(II)-Complex

Zeitschrift für Naturforschung B ◽

10.1515/znb-1992-0411 ◽

1992 ◽

Vol 47 (4) ◽

pp. 517-525 ◽

Cited By ~ 13

Author(s):

Thomas G. Meyer ◽

Peter G. Jones ◽

Reinhard Schmutzler

Keyword(s):

Crown Ether ◽

Single Crystal ◽

Diffraction Study ◽

Planar Geometry ◽

Boat Conformation ◽

Staudinger Reaction ◽

X Ray Diffraction ◽

X Ray ◽

New Synthesis ◽

Square Planar

A new synthesis for 2-chloro-1,3,5-trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinane (1) is described. Chlorine-fluorine exchange in 1 by means of sodium fluoride in acetonitrile in the presence of catalytic amounts of a crown ether furnished 2-fluoro-1,3,5-trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinane (2). The synthesis of the bromine and iodine analogues, 3 and 4, by metathesis of 1 with the appropriate trimethylsilyl halides, Me3SiBr and Me3SiI, respectively, is also described. The syntheses of an iron(0)tetracarbonyl complex (5) and of a dichloroplatinum( II) complex (6) are reported. A single crystal X-ray diffraction study was conducted on 6. [P21/c, a = 1161.3(3), b = 1423.2(3), c = 1247.7(3) pm, β = 109.42(2)°, R = 0.028], There are deviations from ideal square planar geometry at platinum. The heterocycles display a flattened boat conformation. A Staudinger reaction of 1 with Me3SiN3 led to the formation of a substituted cyclotriphosphazene.

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Synthesis, Crystal Structure and Magnetic Properties of a (μ-Hydroxo)(μ-Pyrazolato) Dicopper(II) Complex

Zeitschrift für Naturforschung B ◽

10.1515/znb-2000-0903 ◽

2000 ◽

Vol 55 (9) ◽

pp. 796-802 ◽

Cited By ~ 8

Author(s):

H. Kara ◽

Y. Elerman ◽

K. Prout

Keyword(s):

Crystal Structure ◽

Magnetic Properties ◽

Variable Temperature ◽

Powdered Sample ◽

X Ray Diffraction ◽

Triclinic Space Group ◽

X Ray ◽

Present Complex ◽

Square Planar ◽

Super Exchange Interaction

Preparation and magnetic properties of a 3,5-dimethylpyrazolate bridged binuclear copper(II) complex [Cu2(L)(3 ,5 -pyz)] (L = 1,3-Bis(2-Hydroxy-5-Chlorosalicylideneamino)propan- 2-ol) is reported. The crystal structure determined by X-ray diffraction methods. (C22H20N4O3CI2CU2), triclinic, space group P1̄, a = 9.622(3), b = 10.921(2), c = 11.420(3) Å, α = 100.73(2), β = 94.04(2), Υ = 108.08(2)°, V = 1110.2(5) Å3, Z = 2. Two copper(II) ions in a square-planar coordination are bridged via alkoxide oxygen and 3,5-dimethyl pyrozolate nitrogen atoms to form a dinuclear unit. The metal coordination sphere is four-coordinate, planar with an N2O2 donor set. The dihedral angle between the two coordination planes is 166.83°. There are significant intermolecular interactions between neighbouring binuclear entities. The shortest intermolecular Cu (1) ... Cu(1)i distance is 3.383(1) Å and the Cu(1) - O ( 1)i distance is 2.666(3) Å (i = 1 -x, -y, 1 - z). The variable-temperature magnetic susceptibility measurement for a powdered sample of the complex was carried out in the temperature range 5 - 350 K and analysed to obtain values of the parameter J in the exchange Hamiltonian ℋ = -2JScu Scu; 2J = -164 cm-1. The magnetic moment at 300 K is about 2.42 μB, and 0.22 μB at 5 K. The weak antiferromagnetism of the present complex is reasonably explained in terms of the orbital countercomplementary effect based on Hoffmann's theory for super-exchange interaction

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Bimetallomesogens: Synthesis and Mesomorphic Properties of Coppercomplexes of 3,3'-(2-hydroxypropane-1,3-diyl)bis(azan-1- yl-1-ylidene)bis(2-(4-alkoxyphenyl)prop-1-en-1-ol)

Key Engineering Materials ◽

10.4028/www.scientific.net/kem.428-429.140 ◽

2010 ◽

Vol 428-429 ◽

pp. 140-143

Author(s):

Chung Jung Chen ◽

Chung K. Lai

Keyword(s):

Copper Complexes ◽

Crystallographic Analysis ◽

Planar Geometry ◽

X Ray Diffraction ◽

Scanning Calorimetry ◽

X Ray ◽

Square Planar ◽

New Type ◽

Optical Textures ◽

Mesomorphic Properties

A new type of 3,3'-(2-hydroxypropane-1,3-diyl) bis(azan-1-yl-1-ylidene)bis(2-(4-alkoxy phenyl)prop-1-en-1-ol) and their copper complexes were prepared and mesomorphic properties characterized. The mesomorphic properties of these copper complexes were studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and powder X-ray diffraction. X-ray structural crystallographic analysis showed that these bimetallic compounds have two copper centers coordinated with central square planar geometry. These molecules all have total two 1a or five alkoxy sidechains 1b appended around the central core. The mesomorphic behavior exhibited was found to be dependent on the sidechain density. All compounds in 1a exhibited smectic mesophases, however, compounds in 1b exhibited hexagonal columnar phases (Colh), which were characterized by optical textures and confirmed by powder x-ray diffraction.

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In-house and synchrotron X-ray diffraction studies of 2-phenyl-1,10-phenanthroline, protonated salts, complexes with gold(III) and copper(II), and an orthometallation product with palladium(II)

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229614001843 ◽

2014 ◽

Vol 70 (3) ◽

pp. 260-266 ◽

Cited By ~ 2

Author(s):

Jeanette A. Krause ◽

Daoli Zhao ◽

Sayandev Chatterjee ◽

Roland Falcon ◽

Kristen Stoltz ◽

...

Keyword(s):

Planar Geometry ◽

Water Molecules ◽

X Ray Diffraction ◽

Compound I ◽

Complex Iv ◽

X Ray ◽

Lattice Water ◽

Square Planar ◽

Salt Complex ◽

Monodentate Complex

Different salts of the 2-phenyl-1,10-phenanthrolin-1-ium cation, (pnpH)+, are obtained by reacting 2-phenyl-1,10-phenanthroline (pnp), C18H12N2, (I), with a variety of anions, such as hexafluoridophosphate, C18H13N2+·PF6−, (II), trifluoromethanesulfonate, C18H13N2+·CF3SO3−, (III), tetrachloridoaurate, (C18H13N2)[AuCl4], (IV), and bromide (as the dihydrate), C18H13N2+·Br−·2H2O, (V). Compound (I) crystallizes withZ′ = 2, with both independent molecules adopting a coplanar conformation. In (II)–(IV), a hydrogen bond exists between the cation and anion, while one of the lattice water molecules serves as a hydrogen-bonded bridge between the cation and anion in (V). Reaction of (I) with HAuCl4gives the salt complex (IV); however, reaction with KAuCl4produces the monodentate complex trichlorido(2-phenyl-1,10-phenanthroline-κN10)gold(III), [AuCl3(C18H12N2)], (VI). Dichlorido(2-phenyl-1,10-phenanthroline-κ2N,N′)copper(II), [CuCl2(C18H12N2)], (VII), results from the reaction of CuCl2·2H2O and (I), in which the CuIIcenter adopts a tetrahedrally distorted square-planar geometry. The pendent phenyl ring twists to a bisecting position relative to the phenanthroline plane. The square-planar PdIIcomplex, bromido[2-(phenanthrolin-2-yl)phenyl-κ3C1,N,N′]palladium(II), [PdBr(C18H11N2)], (VIII), is obtained from the reaction of (I) with [PdCl2(cycloocta-1,5-diene)], followed by addition of bromine. A coplanar geometry for the pendent ring is adopted as a result of the tridentate bonding motif.

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Coordination chemistry of dimethylgold(III) and methylmercury(II). Synthesis, 1H N.M.R. and structural studies of Poly(pyrazol-1-yl)borate complexes

Australian Journal of Chemistry ◽

10.1071/ch9831107 ◽

1983 ◽

Vol 36 (6) ◽

pp. 1107 ◽

Cited By ~ 27

Author(s):

AJ Canty ◽

NJ Minchin ◽

JM Patrick ◽

AH White

Keyword(s):

Coordination Chemistry ◽

Variable Temperature ◽

Gold Atom ◽

Pyrazole Ring ◽

Structural Studies ◽

Crystal Data ◽

X Ray Diffraction ◽

X Ray ◽

Square Planar ◽

Borate Complexes

Dimethylgold(III) and methylmercury(II) form complexes Me2AuL and MeHgL where L are poly-(pyrazol-1-yl)borate ligands [HB(pz)3]- and [B(pz)4]-. The structure of Me,Au{HB(pz)3} has been determined by single-crystal X-ray diffraction at 295 K and refined by least-squares methods to R 0.056 for 2194 independent 'observed' reflections. This complex has square-planar coordination for the gold atom involving two coordinated pyrazole rings and one uncoordinated ring, in contrast to the isoelectronic cation [Me2Au{(pz)3CH)]+ which has square planar coordination with a weak axial Au . .N interaction. Variable temperature 1H n.m.r. spectra in CD2Cl2 indicate presence of rapid equilibria between pyrazole ring environments at ambient temperature and, for the MeHgII complexes, down to -90�C. For the Me2AuIII complexes spectra at -90�C indicate presence of pyrazole ring environments in ratios 2 : 1 (L = [HB(pz)3]-) and 2 : 1 : 1 (L = [B(pz)4]-). Crystal data for Me2Au{HB(pz)3}: rhombohedral, space group R3c, a 17.98(1) �, α 117.98(5)�, Z 18.

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Coordination of a triazine ligand with CuII and AgI investigated by spectral, structural, theoretical and docking studies

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229619011719 ◽

2019 ◽

Vol 75 (10) ◽

pp. 1389-1397

Author(s):

Farzin Marandi ◽

Keyvan Moeini ◽

Harald Krautscheid

Keyword(s):

Hydrogen Bonds ◽

Density Functional ◽

Docking Studies ◽

Planar Geometry ◽

X Ray Diffraction ◽

Aromatic Rings ◽

X Ray ◽

Square Planar ◽

Binuclear Structure ◽

Ft Ir

Two complexes of 5-phenyl-3-(pyridin-2-yl)-1,2,4-triazine (PPTA), namely (ethanol-κO)bis(nitrato-κO)[5-phenyl-3-(pyridin-2-yl-κN)-1,2,4-triazine-κN 2]copper(II), [Cu(NO3)2(C14H10N4)(C2H6O)] or [Cu(NO3)2(PPTA)(EtOH)] (1), and bis[μ-5-phenyl-3-(pyridin-2-yl)-1,2,4-triazine]-κ3 N 1:N 2,N 3;κ3 N 2,N 3:N 1-bis[(nitrato-κO)silver(I)], [Ag2(NO3)2(C14H10N4)2] or [Ag2(NO3)2(μ-PPTA)2] (2), were prepared and characterized by elemental analysis, FT–IR spectroscopy and single-crystal X-ray diffraction. The X-ray structure analysis of 1 revealed a copper complex with square-pyramdial geometry containing two O-donor nitrate ligands along with an N,N′-donor PPTA ligand and one O-donor ethanol ligand. In the binuclear structure of 2, formed by the bridging of two PPTA ligands, each Ag atom has an AgN3O environment and square-planar geometry. In addition to the four dative interactions, each Ag atom interacts with two O atoms of two nitrate ligands on adjacent complexes to complete a pseudo-octahedral geometry. Density functional theory (DFT) calculations revealed that the geometry around the Cu and Ag atoms in 1 opt and 2 opt (opt is optimized) for an isolated molecule is the same as the experimental results. In 1, O—H...O hydrogen bonds form R 1 2(4) motifs. In the crystal network of the complexes, in addition to the hydrogen bonds, there are π–π stacking interactions between the aromatic rings (phenyl, pyridine and triazine) of the ligands on adjacent complexes. The ability of the ligand and complexes 1 and 2 to interact with ten selected biomacromolecules (BRAF kinase, CatB, DNA gyrase, HDAC7, rHA, RNR, TrxR, TS, Top II and B-DNA) was investigated by docking studies. The results show that the studied compounds can interact with proteins better than doxorubicin (except for TrxR and Top II).

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E/Z Isomerization of 3-Hydrazonocamphor Promoted by Coordination to Palladium or Platinum

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20070649 ◽

2007 ◽

Vol 72 (5-6) ◽

pp. 649-665 ◽

Cited By ~ 8

Author(s):

M. Fernanda N. N. Carvalho ◽

Ana S. D. Ferreira ◽

João L. Ferreira da Silva ◽

Luís F. Veiros

Keyword(s):

Free Ligand ◽

Intramolecular Hydrogen Bonding ◽

Planar Geometry ◽

Spectroscopic Techniques ◽

X Ray Diffraction ◽

X Ray ◽

Square Planar ◽

Intramolecular Hydrogen ◽

C Nmr

3-Hydrazonocamphor, 3-(RR1NN)C10H14O (R = Me, R1 = H), undergoes intramolecular hydrogen bridging by coordination to platinum or palladium. This effect is evidenced by considerable decrease in the ν(C=O) frequency (compared to the free ligand) in the IR spectra of the complexes [MCl2L2] (M = Pd, Pt; L = 3-(RR1NN)C10H14O) as well as by the magnetic non- equivalence of the two ligands, as revealed by 13C NMR. DFT calculations indicate that coordination of 3-(Me(H)NN)C10H14O promotes E/Z isomerization of the hydrazono group of the ligand, inducing formation of intramolecular hydrogen bonding and corresponding stabilization of the complex. Characterization of the complexes [MCl2L2] (M = Pt; L: R, R1 = Me (1), R = Me, R1 = H (2) and M = Pd; L: R = Me, R1 = H (3)) was performed by analytical and spectroscopic techniques. Redox properties of the 3-hydazonocamphors and their complexes were studied by cyclic voltammetry. The structure of trans-[PtCl2{3-(Me2NN)C10H14O}2] was determined by single-crystal X-ray diffraction analysis. The complex has square-planar geometry and crystallizes in the tetragonal P43 space group.

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The crystal structure of cis-chlorobis(triethylphosphine)-1,8-naphthyridineplatinum(II) tetrafluoroborate, [PtCl(PEt3)2(naph)]BF4, a complex containing a monodentate 1,8-naphthyridine ligand

Canadian Journal of Chemistry ◽

10.1139/v78-072 ◽

1978 ◽

Vol 56 (4) ◽

pp. 450-455 ◽

Cited By ~ 22

Author(s):

Gordon W. Bushnell ◽

Keith R. Dixon ◽

Masood A. Khan

Keyword(s):

Crystal Structure ◽

Variable Temperature ◽

X Ray Diffraction ◽

Nmr Studies ◽

Interatomic Distances ◽

X Ray ◽

Heterocyclic Ligand ◽

Square Planar ◽

Cell Dimensions ◽

R Value

The crystal structure of cis-chlorobis(triethylphosphine)-1,8-naphthyridineplatinum(II) tetrafluoroborate has been determined by single crystal X-ray diffraction and refined to an R-value of 0.063. The cell dimensions are a = 1.4246, b = 1.2676, c = 1.6530 nm, β = 115.66°. The space group is P21/c with 4 molecules per unit cell, and the measured density is 1.665 g cm−3. The structure is essentially a 4-coordinate square planar platinum(II) complex containing monodentate 1,8-naphthyridine. Interatomic distances to platinum are: Pt—Cl, 236.6(4); Pt—P(1), 225.4(4); Pt—P(2), 225.2(4); Pt—N(1), 208.3(11); and Pt—N(2), 304.5(14) pm. The structure is discussed in relation to variable temperature nmr studies of solutions, which indicate fluxional behaviour of the heterocyclic ligand.

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Unprecedented Dinuclear CuII N,O-Donor Complex: Synthesis, Structural Characterization, Fluorescence Property, and Hirshfeld Analysis

Crystals ◽

10.3390/cryst9120607 ◽

2019 ◽

Vol 9 (12) ◽

pp. 607 ◽

Cited By ~ 38

Author(s):

Yin-Xia Sun ◽

Ying-Qi Pan ◽

Xin Xu ◽

Yang Zhang

Keyword(s):

Crystallographic Analysis ◽

Hirshfeld Surface ◽

Planar Geometry ◽

Supramolecular Network ◽

X Ray Diffraction ◽

Tetragonal Pyramid ◽

X Ray ◽

Square Planar ◽

Elemental Analyses ◽

Hirshfeld Analysis

An unprecedented dinuclear CuII complex, [Cu2(L2)2], derived from a salamo-like chelating ligand H2L2, was produced by the cleavage of a newly synthesized, half-salamo-like ligand HL1 (2-[O-(1-ethyloxyamide)]oxime-3,5-dichloro-phenol). This was synthesized and characterized by elemental analyses, IR, UV–Vis and fluorescent spectra, single crystal X-ray diffraction analysis, and Hirshfeld surface analysis. X-ray crystallographic analysis indicated that the two CuII (Cu1 and Cu2) ions bore different (N2O3 and N2O2) coordination environments, the penta-coordinated Cu1 ion possessed a slightly twisted tetragonal pyramid geometry with the τ value τ = 0.004, and the tetra-coordinated Cu2 ion showed a slightly twisted square planar geometry. Interestingly, one oxime oxygen atom participated in the coordination reported previously. Moreover, an infinite two-dimensional layered supramolecular network was formed. Compared with HL1, the CuII complex possessed the characteristic of fluorescence quenching.

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