scholarly journals Transition metal complexes with pyrazole-based ligands, Part 29: Reactions of zinc(II) and mercury(II) thiocyanate with 4-acetyl-3-amino-5-methylpyrazole

2009 ◽  
Vol 74 (11) ◽  
pp. 1259-1271 ◽  
Author(s):  
Zeljko Jacimovic ◽  
Goran Bogdanovic ◽  
Berta Holló ◽  
Vukadin Leovac ◽  
Katalin Szécsényi-Mészáros
Keyword(s):  
Transition Metal Complexes ◽  
Zinc Complex ◽  
Ammonium Thiocyanate ◽  
Molecular Structures ◽  
Coordination Geometry ◽  
Ethanolic Solution ◽  
Tetrahedral Geometry ◽  
X Ray ◽  
Planar Form ◽  
Monodentate Coordination

The work is concerned with the crystal and molecular structures of zinc(II) and mercury(II) complexes with 4-acetyl-3-amino-5-methyl-pyrazole (aamp) of the coordination formulae [Zn(NCS)2(aamp)2[ and (Haamp)2[Hg(SCN)4]. The zinc(II) complex was obtained by the reaction of a warm methanolic solution of aamp with a mixture of zinc(II) nitrate and ammonium thiocyanate, whereas the mercury(II) complex was prepared by the reaction of a warm ethanolic solution of aamp and a warm, slightly acidified aqueous solution of [Hg(SCN)4]2-. Both complexes have a tetrahedral geometry, which in the case of zinc complex is formed by monodentate coordination of two aamp molecules and two isothiocyanate groups. The Zn(II) and Hg(II) atoms have significantly deformed coordination geometry. In both crystal structures the pyrazole derivative has a planar form, probably stabilized by an intramolecular N-H???O hydrogen bond. Apart from the X-ray structural analysis, the isolated complexes were characterized by elemental analysis, IR spectroscopy, conductometric measurements and thermal analysis.

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.

Übergangsmetallkomplexe mit Schwefelliganden, LXXIII. Diastereospezifische Dichlormethylierung schwefelreicher [RuII(SRR′)(PPh3)′S4]-Komplexe (SRR′ = einzähniger Thioether- oder Thiol-Ligand; ′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethan(2-)) / Transition Metal Complexes with Sulfur Ligands, LXXIII. Diastereospecific Dichloromethylation of Sulfur Rich [RuII(SRR′)(PPh3)′S4] Complexes (SRR′ = Monodentate Thioether or Thiol Ligand;′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethane(2-))

1991 ◽  
Vol 46 (12) ◽  
pp. 1585-1592 ◽  
Author(s):  
Dieter Sellmann ◽  
Peter Lechner ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Molecular Structures ◽  
X Ray ◽  
X Ray Crystallography ◽  
Thiol Ligand

Under exclusion of air the thioether and thiol complexes [Ru(SRR′)(PPh3)′S4′] (′S4′2- = 1,2-bis(2-mercaptophenylthio)ethane (2—)) easily react with CHCl3 yielding [Ru(Cl)(PPh3)(′S4′—CHCl2)] in which one thiolato atom of the ′S4′ ligand is diastereospecifically dichloromethylated. In the presence of air, however, [RuIII(Cl)(PPh3)′S4′] is formed.The molecular structures of [Ru(Cl)(PPh3)(′S4′-CHCl2)] · 2CHCl3 and [RuIII(Cl)(PPh3)′buS4′] have been determined by X-ray crystallography. ′buS4′2- (= 1,2-bis(3,5-di(t-butyl)-2-mercaptophenylthio)ethane(2-)) is the t-butyl derivative of the ′S4′ ligand. Reasons for observed diastereospecifity of alkylation are discussed.

Kupfer(I)-Komplexe mit ungesättigten Stickstoffliganden, V / Kupfer(I)-Komplexe mit Diazadienen als Chelate und Brücken: Röntgenstrukturenuntersuchungen an (DAD)Cu(μ-Cl)2Cu(DAD), [(DAD)2Cu]⁺ (CuCl2)-, (DAD)CuCl, [μ-(DAD)2Cu5Cl5]n und [μ-(DAD)Cu(OTf)]n (DAD = Diazadien) / Copper(I) Complexes with Unsaturated Nitrogen Ligands, V Copper(I) Complexes with Chelating and Bridging Diazadienes: X-Ray Diffraction Studies of (DAD)Cu(μ-Cl)2Cu(DAD), [(DAD)2Cu]+ (CuCl2)-, (DAD)CuCl, [μ-(DAD)2Cu5Cl5]n and [μ-(DAD)Cu(OTf)]n (DAD = Diazadiene)

1990 ◽  
Vol 45 (10) ◽  
pp. 1369-1382 ◽  
Author(s):  
Heindirk tom Dieck ◽  
Lutz Stamp
Keyword(s):  
Coordination Polymer ◽  
Molecular Complexes ◽  
Molecular Structures ◽  
Coordination Geometry ◽  
Halide Ions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Nitrogen Ligands ◽  
Crystal And Molecular Structures ◽  
Irregular Geometries

Diazadienes RN = CR′-CR′ = NR (DAD) form molecular complexes with copper(I) halides of composition (DAD)CuX, the structures of which vary from [(DAD)2Cu]+(CuCl2)⁻ with a non-tetrahedral bis(chelated) cation, over [(DAD)CuCl]2 with asymmetrically bridging chloro ligands to planar three-coordinate (DAD)CuCl. The composition of the isolated complexes depends on the relative concentrations or on the solvent. The “soft” coordination geometry of copper is underlined by the structure of the coordination polymer of composition (DAD)2Cu5Cl5, in which Cu atoms of coordination number 2, 3 and 4 and very irregular geometries are encountered and where the DAD ligands are exclusively bridging. Halide ions and sp2-nitrogen donors are very competitive. Bridging DAD ligands are also encountered in (DAD)Cu-Y with the less nucleophilic anions trifluoromethane-sulphonate or perchlorate. Crystal and molecular structures are established for all these coordination geometries and the causes are discussed for the coordination flexibility of copper(I)

Cyclopentadienyl-Ruthenium and -Osmium Chemistry. XL. X-Ray Crystal Structures of MBr (PPh3)2(η-C5H5).CH2Cl2 (M = Ru, Os)

1995 ◽  
Vol 48 (11) ◽  
pp. 1887 ◽  
Author(s):  
MI Bruce ◽  
PJ Low ◽  
BW Skelton ◽  
ERT Tiekink ◽  
A Werth ◽  
...  
Keyword(s):  
Structural Parameters ◽  
Molecular Structures ◽  
Coordination Geometry ◽  
Chloro Complexes ◽  
Triclinic Space Group ◽  
Full Matrix ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Cell Dimensions ◽  
Unit Cell Dimensions

The crystal and molecular structures of MBr (PPh3)2(η-C5H5).CH2Cl2 (M = Ru and Os) have been determined. A revised synthesis of the bromo osmium complex is given. The coordination geometry about the metal atom is based on a distorted octahedron with one face being occupied by the cyclopentadienyl group [average Ru -C(Cp) 2.214(3), Os-C(Cp) 2.177(3)Ǻ] and the other by the bromide [ Ru -Br 2.5683(8), Os-Br 2.5438(9)Ǻ] and the two phosphorus atoms [ Ru -P 2.323(2), 2.329(1); Os-P 2.290(2), 2.297(2)Ǻ]. Structural parameters are compared with those of the corresponding chloro complexes and differ only minimally. Crystals of MBr (PPh3)2(η-C5H5).CH2Cl2 are triclinic, space group Pī , with unit cell dimensions ( Ru [Os]): a 14.374(5) [14.276(4)], b 14.057(4) [13.959(3)], c 10.012(5) [9.903(3)]Ǻ, α 99.43(3) [99.79(2)], β 105.60(3) [105.74(2)], γ 100.42(3) [100.39(2)]°, V 1868(1) [1817.7(9)] Ǻ3, Z 2. The structures were refined by a full-matrix least-squares procedure to R 0.050 [0.036] for 7365 [5108] reflections with I ≥ 3σ(I).

Darstellung und Kristallstrukturen einiger Übergangsmetall-Komplexverbindungen mit Liganden mit dem 4,5-Benzo-3-methyl-1,3,2-oxazaphosphorinan-6-on-Gerüst / Synthesis and X-Ray Crystal Structures of Some Transition-Metal Complexes Involving Ligands with the 4,5-Benzo-3-methyl-1,3,2-oxazaphosphorinan-6-one Framework

1994 ◽  
Vol 49 (11) ◽  
pp. 1481-1493 ◽  
Author(s):  
Axel Fischer ◽  
Ion Neda ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Transition Metal ◽  
Single Crystal ◽  
Transition Metal Complexes ◽  
Nmr Spectra ◽  
Coordination Geometry ◽  
X Ray ◽  
Distorted Octahedral Coordination ◽  
Envelope Conformation ◽  
Square Planar ◽  
Distorted Octahedral

4,5-Benzo-2-diethylamino-3-methyl-1,3,2-oxazaphosphorinan-6-one 1 and 4,5-benzo-2-[bis- (2-chlorethyl)amino]-3-methyl-1,3,2-oxazaphosphorinan-6-one 3 reacted with dichloro- (cycloocta-1,5-diene)platinum(II) [(COD)PtCl2] to give the ds-dichloro-platinum(II) com­plexes 2 and 4, respectively. The reaction of 1 with tricarbonyl(cycloheptatriene)molybdenum(0) led to a mixture of isomers including fac-tris-(4,5-benzo-2-diethylamino-3-methyl- 1,3,2-oxazaphosphorinan-6-one)tricarbonylmolybdenum(0) 5. The reaction of 4,5-benzo- 2-acetylamino-3-methyl-1,3,2-oxazaphosphorinan-6-one 6 with dichloro(cycloocta-1,5-diene)- platinum(II) furnished the cis-complex 7. 4,5-Benzo-2-fluoro-3-methyl-1,3,2-oxazaphosphorinan-6-one 8 reacted with both tetracarbonyl(norbornadiene)molybdenum(0) and dichloro- (cycloocta-1,5-diene)platinum(II) to form the cis-complexes 9 and 10. 31P-31P coupling con­stants from the 31P NMR spectra for the complexes 2, 4 and 9 are reported. The structures of 5, 7, 9 and 10 were established by single crystal X-ray analysis. All ligands coordinate via phosphorus only. The structure of 5 shows strongly distorted octahedral coordination geome­try associated with the presence of three bulky ligands. The Mo-P bond lengths in 5 are, for the same reason, significantly longer than in 9. The heterocycles of the ligands in 5 do not show the expected envelope conformation but are almost planar. The platinum(II) complex 7 shows crystallographic C2-symmetry, the coordination geometry at platinum being almost ideally square-planar. The same coordination geometry is observed for 10, the ligands of which possess the expected envelope conformation with phosphorus out of the plane.

Übergangsmetallkomplexe mit Schwefelliganden, LXXV / Transition Metal Complexes with Sulfur Ligands, LXXV

1991 ◽  
Vol 46 (12) ◽  
pp. 1593-1600 ◽  
Author(s):  
Dieter Sellmann ◽  
Stefan Fünfgelder ◽  
Falk Knoch
Keyword(s):  
Reaction Mechanism ◽  
Transition Metal Complexes ◽  
Coordination Geometry ◽  
Chain Reaction ◽  
Radical Chain ◽  
X Ray ◽  
Square Planar ◽  
Product Forms ◽  
Radical Chain Reaction ◽  
Template Reaction

[Ni(′NHS′4)]2 (′NHS′42- = 2,2′-bis(2-mercaptophenylthio)diethylamine(2-)) was synthesized from Ni(ac)2 and Na2—′NHS′4 and characterized by X-ray structure analysis. In the solid state [Ni(′NHS′4)]2 contains two pseudooctahedral [Ni(′NHS′4)] fragments bridged via thiolate donors, in DMF solution at 110 °C it dissociates into mononuclear entities. The product of the template reaction between [Ni(′S′2)2]2- (′S′22- = 1,2-benzenedithiolate) and (BrC2H4)2NH was shown to contain an as yet unidentified by-product in addition to [Ni(′NHS′4)]2. Pure [Ni(′NHS′4)]2 does not react with pyridine, but the template product forms [Ni(Py)2(′S′2)] which has a square planar coordination geometry with the pyridine rings perpendicular to the NiS2N, plane.Investigation of the template formation of [Ni(′NHS′4)]2 provided evidence that the reaction of [Ni(′S′2)2]2- with (BrC2H4)2NH involves radicals, suggesting a radical chain reaction mechanism.

scholarly journals Coordination Chemistry of Ru(II) Complexes of an Asymmetric Bipyridine Analogue: Synergistic Effects of Supporting Ligand and Coordination Geometry on Reactivities

Molecules ◽  
2019 ◽  
Vol 25 (1) ◽  
pp. 27
Author(s):  
Komi Akatsuka ◽  
Ryosuke Abe ◽  
Tsugiko Takase ◽  
Dai Oyama
Keyword(s):  
Coordination Compounds ◽  
Synergistic Effects ◽  
Electrochemical Analysis ◽  
Molecular Structures ◽  
Coordination Geometry ◽  
Polypyridyl Ligands ◽  
X Ray ◽  
Thermal Reactions ◽  
X Ray Crystallography ◽  
Steric Configuration

The reactivities of transition metal coordination compounds are often controlled by the environment around the coordination sphere. For ruthenium(II) complexes, differences in polypyridyl supporting ligands affect some types of reactivity despite identical coordination geometries. To evaluate the synergistic effects of (i) the supporting ligands, and (ii) the coordination geometry, a series of dicarbonyl–ruthenium(II) complexes that contain both asymmetric and symmetric bidentate polypyridyl ligands were synthesized. Molecular structures of the complexes were determined by X-ray crystallography to distinguish their steric configuration. Structural, computational, and electrochemical analysis revealed some differences between the isomers. Photo- and thermal reactions indicated that the reactivities of the complexes were significantly affected by both their structures and the ligands involved.

Coordination compounds containing a novel tridentate pyrazolylgallate ligand. X-ray structures of Me2Ga(μ-OH)(μ-Me2pz)GaMe2•HOCH2Me2pz and [Me2Ga(pz)(OCH2pz)]2Ni (pz = N2C3H3)

1988 ◽  
Vol 66 (1) ◽  
pp. 101-108 ◽  
Author(s):  
Arthur Mar ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Transition Metal Complexes ◽  
Heavy Atom ◽  
Direct Reaction ◽  
Coordination Geometry ◽  
The Novel ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Normal Bond ◽  
Cis Isomer

The syntheses of the novel anionic tridentate dimethyl(pyrazol-1-yl)(1-oxymethylpyrazolyl)gallate ligand and representative transition metal complexes thereof are reported. The direct reaction of Me3Ga with 1-hydroxymethyl-3,5-dimethylpyrazole leads to the isolation of Me2Ga(μ-OH)(μ-Me2pz)GaMe2•HOCH2Me2pz. Crystals of (μ-hydroxy)(μ-3,5-dimethylpyrazolyl)bis(dimethylgallium) 1-hydroxymethyl-3,5-dimethylpyrazole solvate are monoclinic, a = 33.105(2), b = 7.3048(7), c = 8.8336(6) Å, β = 97.474(7)°, Z = 4, space group P21/n, and those of bis[dimethyl(pyrazol-1-yl)(1-oxymethylpyrazolyl)gallato-N2,N2′,O]nickel(II) are monoclinic, a = 9.6345(3), b = 14.2731(6), c = 18.6356(7) Å, β = 99,660(3)°, Z = 4, space group P21/c. Both structures were solved by conventional heavy atom methods and were refined by full-matrix least-squares procedures to R = 0.044 and 0.037 for 2660 and 3904 reflections with I ≥ 3σ(I), respectively. Mean bond lengths in Me2Ga(μ-OH)(μ-Me2pz)GaMe2•HOCH2Me2pz are Ga—O = 1.918(11), Ga—N = 2.001(5), and Ga—C = 1.955(5) Å. Fac-[Me2Ga(pz)(OCH2pz)]2Ni crystallizes as an all-cis isomer with normal bond lengths and angles at Ga and Ni—O = 1.918(3) and 1.927(3), Ni—N = 2.030(4)–2.111(4) Å. The coordination geometry about Ni is irregular pseudo-octahedral with evidence of both steric and structural trans effects.

scholarly journals Transition metal complexes with pyrazole based ligands, part 27: Structural and thermal characterization of cobalt(II) halide and pseudohalide complexes with 4-acetyl-3-amino-5-methylpyrazole

2007 ◽  
Vol 72 (12) ◽  
pp. 1281-1293 ◽  
Author(s):  
Vukadin Leovac ◽  
Zoran Tomic ◽  
Katalin Mészáros-Szécsényi ◽  
Ljiljana Jovanovic ◽  
Milan Joksovic
Keyword(s):  
Thermal Decomposition ◽  
Solid State ◽  
Transition Metal Complexes ◽  
Thermal Characterization ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Vis Spectroscopy

The crystal and molecular structures of four tetrahedral structurally similar [Co(aamp)2X2] complexes (aamp = 4-acetyl-3-amino-5-methylpyrazole, X = Cl, Br, I and NCS) were determined by X-ray diffraction analysis and are discussed in detail. It was found that the different capacity of the ligand X (NCS vs. Cl, Br, I) for the formation of non-bonding contacts influence the mode of molecular association in the solid state. The complexes were characterized by UV-Vis spectroscopy. The first step of the thermal decomposition of the compounds was checked and is discussed in the view of the IR spectrum of the intermediate isolated from [Co(aamp)2Br2] by the quasi-isothermal technique.

Copper(II) bis(4,4,4-trifluoro-1-phenylbutane-1,3-dionate) complexes with pyridin-2-one, 3-hydroxypyridine and 3-hydroxypyridin-2-one ligands: molecular structures and hydrogen-bonded networks

2017 ◽  
Vol 73 (11) ◽  
pp. 960-967 ◽  
Author(s):  
Franc Perdih
Keyword(s):  
Solid State ◽  
Molecular Structures ◽  
Complex Iii ◽  
Two Dimensional ◽  
Metal Centre ◽  
X Ray ◽  
Graph Set ◽  
Solid State Structures ◽  
Monodentate Coordination ◽  
Hydrogen Bonded

Copper(II) bis(4,4,4-trifluoro-1-phenylbutane-1,3-dionate) complexes with pyridin-2-one (pyon), 3-hydroxypyridine (hpy) and 3-hydroxypyridin-2-one (hpyon) were prepared and the solid-state structures of (pyridin-2-one-κO)bis(4,4,4-trifluoro-3-oxo-1-phenylbutan-1-olato-κ2 O,O′)copper(II), [Cu(C10H6F3O2)2(C5H5NO)] or [Cu(tfpb-κ2 O,O′)2(pyon-κO)], (I), bis(pyridin-3-ol-κO)bis(4,4,4-trifluoro-3-oxo-1-phenylbutan-1-olato-κ2 O,O′)copper(II), [Cu(C10H6F3O2)2(C5H5NO)2] or [Cu(tfpb-κ2 O,O′)2(hpy-κO)2], (II), and bis(3-hydroxypyridin-2-one-κO)bis(4,4,4-trifluoro-3-oxo-1-phenylbutan-1-olato-κ2 O,O′)copper(II), [Cu(C10H6F3O2)2(C5H5NO2)2] or [Cu(tfpb-κ2 O,O′)2(hpyon-κO)2], (III), were determined by single-crystal X-ray analysis. The coordination of the metal centre is square pyramidal and displays a rare example of a mutual cis arrangement of the β-diketonate ligands in (I) and a trans-octahedral arrangement in (II) and (III). Complex (II) presents the first crystallographic evidence of κO-monodentate hpy ligation to the transition metal enabling the pyridine N atom to participate in a two-dimensional hydrogen-bonded network through O—H...N interactions, forming a graph-set motif R 2 2(7) through a C—H...O interaction. Complex (III) presents the first crystallographic evidence of monodentate coordination of the neutral hpyon ligand to a metal centre and a two-dimensional hydrogen-bonded network is formed through N—H...O interactions facilitated by C—H...O interactions, forming the graph-set motifs R 2 2(8) and R 2 2(7).

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