Synthetic and Structural Studies of Binuclear Organopalladium(II) Complexes Including a Bis(pyridin-2-yl)phenylmethyl Complex With Four- and Eight-Membered Palladocycle Rings, trans(N,N)-(Pd(μ-Py2PhC-N,N',C')Cl)2.½CH2Cl2.½Me2CO

1988 ◽  
Vol 41 (5) ◽  
pp. 651 ◽  
Author(s):  
AJ Canty ◽  
NJ Minchin ◽  
LM Engelhardt ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Ethyl Acetate ◽  
Column Chromatography ◽  
Isolation Procedure ◽  
Addition Reactions ◽  
Structural Studies ◽  
Monoclinic System ◽  
Space Group ◽  
X Ray ◽  
Square Planar ◽  
System 2

The byridin-2-yl) phenylchloromethanes PyPh2CCl and Py2PhCCl undergo oxidative addition reactions with bis ( dibenzylideneacetone )palladium(0) to form {Pd(PyPh2C) Cl }2 (1) and {Pd(Py2PhC)C}2.�2CH2Cl2.�Me2CO (2), respectively. n.m.r , studies of (1) in CDCl3 indicate presence of an equilibrium between two isomers, involving the ligand (pyridin-2-yl ) diphenylmethyl in η3-coordination, {Pd(η3-PyPh2C)(μ- Cl )}2. Complex (2) has two bis (pyridin-2-yl) phenylmethyl groups present as bridging N,C′- ligands , with the groups also N,C- bidentate to each palladium, to form a binuclear compex containing four- and eight- membered palladocycles: PdC(CN)CNPdC(CN)CNBoth palladium(II) centres in (2) have square-planar 'trans-PdCN2Cl' coordination, so that (2) may be represented as trans(N,N)-{Pd(μ- Py2PhC-N,N′, C′) Cl }2.�CH2Cl2.�Me2CO. A complex similar to (2), trans(N,N)-{Pd(μ- PyPhCH -N,C?)( γmpy ) Cl }2.CH2Cl2 (3), forms on reaction of the lithium derivative of 2-benzylpyridine, Li( PyPhCH ), with dichlorobis (4-methylpyridine)palladium(II); (3) reacts with excess 2-benzylpyridine with displacement of γmpy to form trans(N,N)-{Pd(μ- PyPhCH -N,C?)(PyPhCH2) Cl }2 (4). In developing an alternative isolation procedure for (3), involving column chromatography with 4% ethyl acetate in chloroform, the coordination complex trans- bis{1-phenyl-1-(pyridin-2-yl)prop-1-en-2-olato-O,N}palladium(II), Pd{( PyPhC )C(Me)O}2 (5), was isolated in low yield. X-Ray structural studies of (2)-(5) have been completed, with all four complexes crystallizing in the monoclinic system; (2): space group P21/c, a 9.649(6), b 21.116(9), c 18.627(7)Ǻ,β 111.42(4)°, Z 4; (3): P21/c, a 13.967(2), b 13.996(3), c 18.886(2)Ǻ, β 98.74(1)°, Z 4; (4): P21/n, a 14.274(9), b 14.584(14), c 20.97(2)Ǻ, β 109.18(5)°, Z 4; (5): P21/c, a 15.184(3), b 7.887(6), c 19.240(2)Ǻ, β 97.51(1)°, Z 4.

Coordination chemistry of thioether–pyridazine macrocycles. I. Synthetic, structural, and spectroscopic studies of Cu(II) and Cu(I) complexes of novel thioether–pyridazine macrocycles that contain two or three pyridazine subunits

1992 ◽  
Vol 70 (7) ◽  
pp. 1886-1896 ◽  
Author(s):  
Liqin Chen ◽  
Laurence K. Thompson ◽  
John N. Bridson
Keyword(s):  
Copper Complexes ◽  
Spin Exchange ◽  
Spectroscopic Studies ◽  
Esr Spectra ◽  
Monoclinic System ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Triclinic System ◽  
Square Planar

The preparations of thioether–pyridazine macrocycles containing three (L1) and two (L2) pyridazine subunits and their copper complexes are described. The ligands are characterized by 1H nuclear magnetic resonance and mass spectrometry and in one case by X-ray crystallography, and the complexes by infrared, electronic, and electron spin resonance (esr) spectra and in some cases by X-ray crystallography. The complex [Cu3(L1)2Cl6]•2CHCl3 (1) crystallized in the triclinic system, space group [Formula: see text] with a = 13.661(2) Å, b = 14.174(3) Å, c = 9.412(2) Å, α = 101.08(2)°, β = 96.94(2)°, γ = 75.76(2)°, V = 1728.2(6) Å3, and Z = 2 (R = 0.056, Rw = 0.048 for 2080 reflections). Two monodentate pyridazine rings in each ligand bind to one square-planar copper centre with the third monodentate pyridazine in each ligand linking the two to the central square-planar copper. The complex [Cu(L2)Cl2] (2) crystallized in the orthorhombic system, space group Pnma, with a = 8.571(1) Å, b = 16.104(3) Å, c = 13.961(2) Å, V = 1927(1) Å3, and Z = 4 (R = 0.037, Rw = 0.033 for 1070 reflections). A cis square-planar structure exists for 2 with monodentate pyridazines. [Cu(L2)2]•(ClO4)2•CH3CN•CHCl3 (5) crystallized in the triclinic system, space group [Formula: see text] with a = 12.888(4) Å, b = 17.462(6) Å, c = 10.906(1) Å, α = 96.07(2)°, β = 104.18(2)°, γ = 94.51(2)°, V = 2352(1) Å3, and Z = 2 (R = 0.053, Rw = 0.044 for 2941 reflections). Two ligands involving monodentate pyridazine rings bind to a square-planar copper(II) centre. The protonated ligand salt [L2H](ClO4)•H2O (6) crystallized in the monoclinic system, space group P21/n, with a = 14.762(4) Å, b = 8.637(5) Å, c = 16.267(4) Å, β = 92.78(2)°, V = 2072(1) Å3, and Z = 4 (R = 0.064, Rw = 0.053 for 1456 reflections). No sulfur coordination is observed in these complexes and there is no apparent spin exchange in the trinuclear derivative.

Synthesis and structural studies of rhodium complexes of phosphorus—sulfur ligands

1986 ◽  
Vol 64 (9) ◽  
pp. 1870-1875 ◽  
Author(s):  
David G. Dick ◽  
Douglas W. Stephan
Keyword(s):  
Single Crystal ◽  
Planar Geometry ◽  
Methyl Groups ◽  
Rhodium Complexes ◽  
Coordination Geometry ◽  
Structural Studies ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
Square Planar

Rhodium complexes of the phosphorus—sulfur ligands, 2-diphenylphosphinoethyl methyl sulfide (MeSP), 1, and 2-diphenylphosphinothiophene (PTH), 2, have been prepared and studied by single crystal X-ray diffraction methods. [Rh(MeSP)2]BF4•H2O, 3, crystallizes in the space group P21/n with a = 16.939(6) Å, b = 17.152(5) Å, c = 12.049(9) Å, β = 106.50(4)°, and Z = 4. The MeSP ligands chelate to Rh yielding a distorted square-planar geometry. The disposition of the methyl groups on the cis sulfur atoms is transoid. Average Rh—P and Rh—S bond distances were found to be 2.225(3) and 2.347(3) Å, respectively. [Rh(PTH)2(COD)]BF4, 4, crystallizes in the space group Cc with a = 15.862(2) Å, b = 15.112(3) Å, c = 16.029(3) Å, β = 103.32(1)°, and Z = 4. The Rh atom in 4 also has essentially a square-planar coordination geometry. 2 does not chelate but rather is monohapto through phosphorus. Rh—P distances of 2.319(3) and 2.378(3) Å and Rh—C distances of 2.17(1), 2.22(1), 2.24(1), and 2.27(1) Å were found. The small variations in the Rh—P and Rh—C bonds distances appear to be a result of steric interactions between 2 and the COD ligand.

scholarly journals Kinetic Analysis of the Thermal Decomposition of Iron(III) Phosphates: Fe(NH3)2PO4 and Fe(ND3)2PO4

2020 ◽  
Vol 21 (3) ◽  
pp. 781
Author(s):  
Isabel Iglesias ◽  
José A. Huidobro ◽  
Belén F. Alfonso ◽  
Camino Trobajo ◽  
Aránzazu Espina ◽  
...  
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Analysis ◽  
Room Temperature ◽  
Isoconversional Methods ◽  
Iron Phosphate ◽  
Dihydrogen Phosphate ◽  
Monoclinic System ◽  
Space Group ◽  
X Ray ◽  
Group A

The hydrothermal synthesis and both the chemical and structural characterization of a diamin iron phosphate are reported. A new synthetic route, by using n-butylammonium dihydrogen phosphate as a precursor, leads to the largest crystals described thus far for this compound. Its crystal structure is determined from single-crystal X-ray diffraction data. It crystallizes in the orthorhombic system (Pnma space group, a = 10.1116(2) Å, b = 6.3652(1) Å, c = 7.5691(1) Å, Z = 4) at room temperature and, below 220 K, changes towards the monoclinic system P21/n, space group. The in situ powder X-ray thermo-diffraction monitoring for the compound, between room temperature and 1100 K, is also included. Thermal analysis shows that the solid is stable up to ca. 440 K. The kinetic analysis of thermal decomposition (hydrogenated and deuterated forms) is performed by using the isoconversional methods of Vyazovkin and a modified version of Friedman. Similar values for the kinetic parameters are achieved by both methods and they are checked by comparing experimental and calculated conversion curves.

Synthesis, structural and magnetic properties of macrocyclic aza-amido binuclear copper(II) complexes

1989 ◽  
Vol 67 (4) ◽  
pp. 662-670 ◽  
Author(s):  
Sanat K. Mandal ◽  
Laurence K. Thompson ◽  
Michael J. Newlands ◽  
Amal K. Biswas ◽  
Bibhutosh Adhikary ◽  
...  
Keyword(s):  
Variable Temperature ◽  
Complex Iii ◽  
Azomethine Nitrogen ◽  
X Ray Diffraction ◽  
Binuclear Copper ◽  
Magnetic Studies ◽  
Monoclinic System ◽  
Space Group ◽  
Pyramidal Geometry ◽  
Square Planar

Binuclear, antiferromagnetically coupled, macrocyclic copper(II) complexes, [Cu2(C28H32N4O4)]•H2O (II) and [Cu2(C36H32N4O4)]•CH3CN•H2O (III), involving asymmetric ligands with two deprotonated amide, two azomethine nitrogen, and two phenoxide donors at the binuclear centre, have been synthesized and characterized by single-crystal X-ray diffraction and variable temperature magnetic studies. Complex II crystallizes in the monoclinic system, space group P21/n, with a = 16.4854(9) Å, b = 7.6005(13) Å, c = 21.1617(11) Å, β = 104.090(5)°, Z = 4, Rf = 0.068 for 2062 significant reflections. The two copper(II) centres have square planar N2O2 donor sets with two phenoxide oxygen atoms bridging the copper centres with a copper–copper separation of 2.898(2) Å. A long copper–oxygen (amide) contact (2.808(10) Å) forms a weak dimer association. Complex III crystallizes in the triclinic system, space group [Formula: see text], with a = 8.7771(9) Å, b = 12.3983(16) Å, c = 15.7299(16) Å, α = 85.003(11)°, β = 84.574(8)°, γ = 76.838(10)°, Z = 2, Rf = 0.041 for 2966 significant reflections. The two copper(II) centres have distorted square-pyramidal geometry involving an N2O2 in plane donor set and two phenoxide oxygen bridges with a copper–copper separation of 3.018(1) Å. The fifth coordination site at each copper centre involves an amide oxygen from a neighbouring molecule (Cu(1)—O 2.371(4), Cu(2)—O 2.413(3) Å) in a staggered intermolecular array. Very strong antiferromagnetic exchange is observed in both cases (−2J = 689 ± 7 cm−1 (II), −2J = 816 ± 8 cm−1 (III)). Keywords: macrocycles, binuclear copper(II) complexes.

Induced chirality-at-metal and diastereoselectivity at Δ/Λ-configured distorted square-planar copper complexes by enantiopure Schiff base ligands: combined circular dichroism, DFT and X-ray structural studies

2014 ◽  
Vol 43 (8) ◽  
pp. 3313-3329 ◽  
Author(s):  
Mohammed Enamullah ◽  
A. K. M. Royhan Uddin ◽  
Gennaro Pescitelli ◽  
Roberto Berardozzi ◽  
Gamall Makhloufi ◽  
...  
Keyword(s):  
Schiff Base ◽  
Circular Dichroism ◽  
Copper Complexes ◽  
Structural Studies ◽  
Schiff Base Ligands ◽  
X Ray ◽  
Square Planar ◽  
Circular Dichroïsm

Übergangsmetallkomplexe mit Schwefelliganden, LXXVI Redox- und Additionsreaktionen von Nickelkomplexen mehrzähniger Thioether-Thiolat-Liganden. Röntgenstrukturanalysen von (NMe4)2[Ni(′S2′)2] und [Ni(′S4 – C3′)(PMe3)] / Transition Metal Complexes with Sulfur Ligands, LXXVI Redox and Addition Reactions of Nickel Complexes with Multidentate Thioether-Thiolato Ligands. X-Ray Structure Determinations of (NMe4)2[Ni(′S2′)2] and [Ni(′S4–C3′)(PMe3)]

1991 ◽  
Vol 46 (12) ◽  
pp. 1601-1608 ◽  
Author(s):  
Dieter Sellmann ◽  
Stefan Fünfgelder ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Nickel Complexes ◽  
Addition Reactions ◽  
Coordination Geometry ◽  
X Ray ◽  
Square Planar ◽  
Structure Determinations

In order to elucidate specific properties of nickel sulfur complexes, redox and addition-elimination reactions of [Ni(′OS4')]2, [Ni(′NHS4')]2, [Ni(′S5')], [Ni('S4—C5')], and [Ni('S4—C3')] were investigated ('OS4′ 2' = 2,2'-bis(2-mercaptophenylthio)diethylether(2—), 'NHS4'2- = 2,2'-bis(2-mercaptophenylthio)diethylamine(2—), 'S5'2- = 2,2'-bis(2-mercaptophenylthio)diethylsulfide(2—), 'S4-C5'2- = 1,5-bis(2-mercaptophenylthio)pentane(2—), 'S4—C3'2- = 1,3-bis(2-mercaptophenylthio)propane(2—)).Cyclovoltammetry proves the complexes to be redox inactive between —1.4 and +0.8 V vs. NHE. Above +0.8 V the complexes are irreversibly oxidized, below —1,4 V desalkylation takes place and [Ni(′S,′)2]2- is formed. An X-ray structure analysis was carried out of (NMe4)2[Ni(′S2')2], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identical to those in the [Ni(′S2')2-] monoanion.The complexes coordinate only phosphines as coligands, but thioether donors simultaneously decoordinate and, dependant of reaction temperature, mono- or trisphosphine complexes are formed. [Ni(′S4—C3')(PMe3)] was characterized by X-ray structure analysis and exhibits a square pyramidal coordination geometry.

Crystallochemistry and structural studies of two newly CaSb0.50Fe1.50(PO4)3 and Ca0.50SbFe(PO4)3 Nasicon phases

2006 ◽  
Vol 21 (1) ◽  
pp. 45-51 ◽  
Author(s):  
Abderrahim Aatiq ◽  
My Rachid Tigha ◽  
Rabia Hassine ◽  
Ismael Saadoune
Keyword(s):  
Solid State ◽  
Room Temperature ◽  
Rietveld Analysis ◽  
Structural Studies ◽  
Hexagonal Cell ◽  
Conventional Solid State Reaction ◽  
Space Group ◽  
X Ray ◽  
Cell Parameters ◽  
Crystallographic Structures

Crystallographic structures of two new orthophosphates Ca0.50SbFe(PO4)3 and CaSb0.50Fe1.50(PO4)3 obtained by conventional solid state reaction techniques at 900 °C, were determined at room temperature from X-ray powder diffraction using Rietveld analysis. The two compounds belong to the Nasicon structural family. The space group is R3 for Ca0.50SbFe(PO4)3 and R3c for CaSb0.50Fe1.50(PO4)3. Hexagonal cell parameters for Ca0.50SbFe(PO4)3 and CaSb0.50Fe1.50(PO4)3 are: a=8.257(1) Å, c=22.276(2) Å, and a=8.514(1) Å, c=21.871(2) Å, respectively. Ca2+ and vacancies in {[Ca0.50]3a[◻0.50]3b}M1SbFe(PO4)3 are ordered within the two positions, 3a and 3b, of M1 sites. Structure refinements show also a quasi-ordered distribution of Sb5+ and Fe3+ ions within the Nasicon framework. Thus, in {[Ca0.50]3a[◻0.50]3b}M1SbFe(PO4)3, each Ca(3a)O6 octahedron shares two faces with two Fe3+O6 octahedra and each vacancy (◻(3b)O6) site is located between two Sb5+O6 octahedra. In [Ca]M1Sb0.50Fe1.50(PO4)3 compound (R3c space group), all M1 sites are occupied by Ca2+ and the Sb5+ and Fe3+ ions are randomly distributed within the Nasicon framework.

Tetrahalogenotellurate(II): Synthese und Kristallstrukturen von Verbindungen mit den Ionen TeX42- (X = Cl, Br, I)/Tetrahalotellurates(II): Syntheses and Crystal Structures of Compounds with TeX42- Ions (X = Cl, Br, I)

1985 ◽  
Vol 40 (2) ◽  
pp. 251-257 ◽  
Author(s):  
Siegfried Pohl ◽  
Wolfgang Saak ◽  
Bernt Krebs
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Acetonitrile Solution ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Square Planar

Abstract The compounds [(C6H5)4As]2 TeCl4 (1), [(C2H5)4 N]2 TeBr4 · CH3CN (2), and [(C2H5)4N]2TeI4 (3) were prepared by the reaction of Te, X2 , and excess (C2H5)4NX (X = Br, I) in acetonitrile solution or by heating of [(C6H5)4 As]2TeCl6 , Te, and (C6H5)4 ASCl for several hours in the same solvent.The structures of 1-3 were determined from single crystal X-ray data.1 crystallizes in the monoclinic space group P21/n with a = 1061.8(2), b = 1614.2(3), c = 1341.7(3) pm, β = 94.21° and Z = 2; 2: tetragonal, P4/mmm, a = 1039.7(2), c = 690.5(1), Z = 1; 3: tetragonal, I4/mmm, a = 1061.7(2), c = 1342.8(4), Z = 2. In 1-3 Te(II) exhibits a square planar coordination. The Te -CI, Te -Br, and Te-I bond lengths were found to be 260.7 (mean), 275.3, and 298.5 pm, respectively.

Darstellung und Röntgenstrukturanalyse von (DichIoro)-(1,3,5,7-tetramethyI-2,4,6,8,9,10-hexathiaadamantan)palladium(II), PdCl2(CH3)4C4S6 Preparation and X-Ray Structure Analysis of (D ichloro)-(l,3,5,7-tetram ethyl-2,4,6,8,9,10-hexathiaadam antane)palladium (II), PdCl2(CH3)4C4S6

1986 ◽  
Vol 41 (4) ◽  
pp. 409-412 ◽  
Author(s):  
Joachim Pickardt ◽  
Norbert Rautenberg
Keyword(s):  
Structure Analysis ◽  
Palladium Complex ◽  
Bond Angle ◽  
Free Ligand ◽  
Lattice Parameters ◽  
Space Group ◽  
X Ray ◽  
Chelating Ligand ◽  
Square Planar

By reaction of PdCl2(C6H5CN) 2 with 1,3,5,7-tetram ethyl-2,4,6,8,9,10-hexathiaadam antane, (CH3)4C4S6, (“TMTA”), the complex PdCl2-TMTA could be obtained. X-ray structure analyses were performed for the free ligand TMTA as well as for the adduct. Both com pounds crystallize monoclinically, space group P21/n, lattice parameters for TMTA are a= 845.9(5), b= 1225.8(7), c= 1314.8(8) pm, ß= 93.28(5)°; for PdCl2-TMTA a= 1262.3(3), b= 1376.3(4), c= 939.1(3) pm, and ß= 92.86(5)°. In the palladium complex TMTA acts as a bidentate chelating ligand. The coordination about the Pd atom is approximately square planar, but the bond angle S -Pd -S is only 76.2°

1,3,5-Triphosphorinane. Synthese und Struktur der Isomeren des 1,3,5-Triphenyl-1,3,5-triphosphorinans/ 1,3,5-Triphosphorinanes. Synthesis and Structure of the Isomers of 1,3,5-Triphenyl-1,3,5-triphosphorinane

2006 ◽  
Vol 61 (5) ◽  
pp. 577-582 ◽  
Author(s):  
Manfred Fild ◽  
Peter G. Jones ◽  
Michael Lorms ◽  
Stefan Jäger
Keyword(s):  
Nmr Spectroscopy ◽  
Single Crystal ◽  
Column Chromatography ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray

The reaction of lithiated Ph(H)PCH2P(H)Ph with (ClCH2)2PPh yields 1,3,5-Triphenyl-1,3,5- triphosphorinane (1) as a mixture of two isomers. The isomers have been separated by column chromatography and characterized by NMR spectroscopy and single crystal X-ray diffraction as the eq-eq-eq (1a) and eq-eq-ax-isomers (1b). (1a) crystallizes with a = 1326.9(3) pm and c = 933.4(3) pm in the rhombohedral space group R3 and displays 3-fold symmetry, showing an eq-eq-eq conformation. (1b) crystallizes in the monoclinic space group P21/c with a = 984.09(12) pm, b = 1757.5(2) pm, c = 1083.13(12) pm, β = 93.329(2)° and displays an ax-eq-eq conformation.

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