The Pd(II) Complex of a Bidentate Di(benzimidazol-2-ylidene) Ligand

2004 ◽  
Vol 59 (5) ◽  
pp. 541-543 ◽  
Author(s):  
F. Ekkehardt Hahn ◽  
Thorsten von Fehrena ◽  
Lars Wittenbecher ◽  
Roland Fröhlich
Keyword(s):  
Structure Analysis ◽  
Mononuclear Complex ◽  
X Ray ◽  
Pale Yellow ◽  
Square Planar

Abstract The pale yellow palladium(II) dicarbene complex cis-[PdI2(L)], 2 (L = 1,3-bis-(3-neopentylbenzimidazol- 2-ylidene)-2,2-dimethylpropane) was synthesized by the reaction of PdI2 with an N1,N1’- 2,2’-dimethylpropane-bridged dibenzotetraazafulvalene 1 in tetrahydrofuran. The X-ray structure analysis revealed a mononuclear complex with a palladium(II) center coordinated in a slightly distorted square-planar fashion by the bidentate carbene ligand and two iodo ligands.

The Pd(II) Complex of a N,N’-Diallylbenzimidazol-2-ylidene Ligand

2004 ◽  
Vol 59 (9) ◽  
pp. 1051-1053 ◽  
Author(s):  
F. Ekkehardt Hahn ◽  
Tania Pape ◽  
Christian Holtgrewe
Keyword(s):  
Structure Analysis ◽  
Mononuclear Complex ◽  
X Ray ◽  
Square Planar

The palladium(II) dicarbene complex trans-[PdBr2(L)2], 2 (L = 1,3-di-(2-propenyl)-benzimidazol- 2-ylidene) was synthesized from 1,3-di-(2-propenyl)-benzimidazolium bromide 1 and Pd(OAc)2 by in situ deprotonation. The X-ray structure analysis revealed a mononuclear complex with a palladium( II) center coordinated in a square-planar fashion by the two carbene functions and two bromo ligands.

Cleavage of a Dibenzotetraazafulvalene to Yield a Rh(I) Carbene Complex

2004 ◽  
Vol 59 (5) ◽  
pp. 544-546 ◽  
Author(s):  
F. Ekkehardt Hahn ◽  
Thorsten von Fehren ◽  
Lars Wittenbecher ◽  
Roland Fröhlich
Keyword(s):  
Double Bond ◽  
Structure Analysis ◽  
Mononuclear Complex ◽  
X Ray ◽  
Carbene Complex ◽  
Square Planar

Abstract The reaction of the dibenzotetraazafulvalene C6H4(NC2H5)2C=C(NC2H5)2C6H4, 1 = 1, with [(COD)Rh(μ-Cl)2Rh(COD)] proceeds via cleavage of the C=C double bond and yields the carbene complex [(COD)RhCl(1)], 2. The X-ray structure analysis shows 2 to be a mononuclear complex with a rhodium(I) center coordinated in a slightly distorted square-planar fashion.

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.

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°

Metallkomplexe von N-(Pyrrol-l-yl)salicylaldiminen und deren Strukturbestimmung mittels Röntgendiffraktometrie und Röntgenabsorptionsspektroskopie (XANES) / Metal Chelates of N -(Pyrrol-l-yl)salicylaldim ines and their Structure D eterm ination by X-Ray Structure Analysis and X -R ay Absorption Spectroscopy (XANES)

1996 ◽  
Vol 51 (6) ◽  
pp. 757-764 ◽  
Author(s):  
A. Bach ◽  
L. Beyer ◽  
T. Gelbrich ◽  
K. H. Hallmeier ◽  
C. Hennig ◽  
...  
Keyword(s):  
Structure Analysis ◽  
Absorption Spectroscopy ◽  
Line Shape ◽  
Metal Chelate ◽  
Molecular Structures ◽  
Chelate Complexes ◽  
X Ray ◽  
3D Metals ◽  
Square Planar ◽  
X Ray Absorption

Abstract A series of three N-(pyrrol-l-yl)salicylaldim ines 1-3 has been prepared an d characterized. Their metal chelate complexes with Cu, Ni and Co are described. The molecular structures of bis[N-(pyrrol-l-yl)salicylaldim inato]copper(lI) la, bis{N-[3-(pyrrol-l-yl)propyl]- salicylaldiminato}nickel(II) 2b and tris{N-[3-(pyrrol-l-yl)propyl]salicylaldiminato}cobalt(III) 2d were determined by X-ray structure analysis. The chelates with tetracoordinated copper and nickel show a square planar coordination with the characteristic trans configuration. The chelate with hexacoordinated cobalt has a meridional coordination sphere. The complexes have also been investigated by X-ray absorption spectroscopy (X̲-ray A̲bsorption N̲ear E̲dge S̲tructure, XANES) at the K edges of the 3d metals. Analyzing the relative intensities of the Is → 3d prepeak and the K edges of the line shape, it was possible to distinguish between planar, tetrahedral and octahedral coordination of the chelates

Übergangsmetallkomplexe mit Schwefelliganden, XC Synthese, Säure/Base- und Redoxreaktionen von [Ni(′N2H2S2′)]: auf der Suche nach Modellkomplexen für die Nickelzentren in Hydrogenasen und CO-Dehydrogenasen. (′N2H2S2′′2- = 1,2-Ethandiamin-N,N′-bis(2-benzolthiolat)(2–)) / Transition Metal Complexes with Sulfur Ligands, XC. Synthesis, Acid Base and Redox Reactions of [Ni(′N2H2S2′)]: A Search for Model Complexes for the Nickel Sites in Hydrogenases and CO-Dehydrogenases. (′Ν2Η2S2′2- = 1,2-Ethanediamine-N,N′-bis(2-benzenethiolate)(2-))

1992 ◽  
Vol 47 (10) ◽  
pp. 1411-1423 ◽  
Author(s):  
Dieter Sellmann ◽  
Werner Prechtel ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Redox Reactions ◽  
Schiff Base Complex ◽  
Nickel Atom ◽  
Consecutive Reaction ◽  
Model Complexes ◽  
X Ray ◽  
Square Planar ◽  
Distorted Octahedral

[Ni(′N2H2S2′)], 1, forms from Ni(II) salts and the tetradentate thiolate-amine ligand ′N2H2S2′2- (= 1,2-ethanediamine-N,N′-bis(2-benzenethiolate)(2-)) [2], or by reduction of the Schiff base complex [Ni(gma)] (gma2- = glyoxal-bis(2-mercaptoanilide(2–))) with NaBH4.Bases easily deprotonate 1 to yield the [Ni(′N2S2′)]2- dianion, which is extremely easily oxidized to give the Ni(II) monoanion [Ni(′N2S2′)]- which was isolated as [AsPh4][Ni(′N2S2′)], 4, and characterized by X-ray structure analysis. 4 contains a distorted square planar NiN2S2 core, in which two thiolate-S and two amido-N donors are surrounding the nickel atom.Deprotonation of 1 was further substantiated by H*/D+ exchange to give [Ni(′N2D2S2′)] and by alkylation. Consecutive reaction of 1 with n-BuLi and CH3I leads to fourfold methylation of 1 yielding [Ni(′N2Me2S2Me2′)I2], 8, while alkylation of 1 by CH3I in the absence of base yields [Ni(′N2H2S2Me2′)I2], 5, in which only the thiolate donors have been alkylated. X-ray structure analysis shows 8 to contain a distorted octahedral NiN2S2I2 core with two sulfur atoms occupying axial trans positions and two nitrogen and two iodine atoms occupying equatorial cis positions. 1 also forms by reaction of [Ni(CO)4] with ′N2H2S2′-H2, which is explained by a series of oxidative addition and reductive elimination reactions.Palladium and platinum homologues [Pd(′N2H2S2′)], 9 and [Pt(′N2H2S2′)], 10, were synthesized from [MC12(COD)] (M = Pd, Pt) and ′N2H2S2′-H2, and exhibit analogous reactivity as 1.

Substituierte 1,2,4-Thiadiazolium-dichloroaurate(I) und -tetra- chloroaurate(III) als Reaktionsprodukte von N-Thiocarbamoyl- benzamidinen mit TetrachIorogold(III)-Verbindungen / Substituted 1,2,4-Thiadiazolium dichloroaurates(I) and -tetrachloroaurates(III) as Products o f the Reaction o f N -Thiocarbam oyl-benzamidines with Tetrachlorogold(III) Compounds

1997 ◽  
Vol 52 (5) ◽  
pp. 620-628 ◽  
Author(s):  
Uwe Schröder ◽  
Rainer Richter ◽  
Jürgen Hartung ◽  
Ulrich Abram ◽  
Lothar Beyer
Keyword(s):  
Ir Spectroscopy ◽  
Structure Analysis ◽  
Elemental Analysis ◽  
Tautomeric Form ◽  
X Ray ◽  
Bond Lengths ◽  
Square Planar ◽  
Ring Position ◽  
C Nmr

Abstract The reactions of N-diethylaminothiocarbonyl-benzamidines Et2N-C(S)-N=C(NHR)-Ph (1: R = Ph, 2: R = C3H7, 3: R = H) with gold(III) compounds were studied. Treatment of 1 and 2 with equivalent amounts of tetrachlorogold acid gives 2,3-substituted 5-diethylamino-1,2,4- thiadiazoliumdichloroaurates(I) (1a, 2a). With tetrachlorogold acid in excess 1 yields 2,3-diphenyl- 5-diethylamino-l,2,4-thiadiazolium-tetrachloroaurate(III) 1b. With 3 and Na[AuCl4] bis(3-phenyl-5- diethylamino-1,2,4-thiadiazolium)-chloride-tetrachloroaurate(III) 3b is produced. The structures of la, 2a and 3b were investigated by X-ray structure analysis. In la and 2a the dichloroaurate(I) ions are linear. In the 1,2,4-thiadiazolium cations the N-C-bond lengths alternate characteristically. In 3b the tetrachloroaurate(III) ion is square planar. The 1,2,4-thiadiazolium cation shows a different alternation of N-C bond lengths in comparison with la and 2a which suggests changes in the thiadiazolium ring in 3b to a tautomeric form as confirmed by the localization of the H atom at the N atom in ring position 4 instead of ring position 2. The structures of 1a, 1b, 2a and 3b were confirmed by elemental analysis, ES-MS, FAB-MS, 1H and 13C NMR and IR spectroscopy.

The Ti(IV) Complex of a Benzannulated N-Heterocyclic Carbene

2004 ◽  
Vol 59 (3) ◽  
pp. 348-350 ◽  
Author(s):  
F. Ekkehardt Hahn ◽  
Thorsten von Fehren ◽  
Roland Fröhlich
Keyword(s):  
Structure Analysis ◽  
Mononuclear Complex ◽  
Equatorial Position ◽  
X Ray ◽  
Carbene Complex ◽  
Trigonal Bipyramidal ◽  
Distorted Trigonal Bipyramidal

The yellow titanium(IV) carbene complex [TiCl4(1)], 2 (1 = N,N’-bis(2,2-dimethylpropyl)benzimidazol-2-ylidene) was synthesized by reaction of TiCl4 and the benzannulated carbene 1 in toluene. The X-ray structure analysis revealed a mononuclear complex with a titanium(IV) center coordinated in a distorted trigonal-bipyramidal fashion by the carbene ligand in an equatorial position and four chloro ligands

Synthesis and Structure of a Tetranuclear Nickel Complex of a 40-Membered Macrocyclic Octaamine-Tetrathiophenolate Ligand

2000 ◽  
Vol 55 (10) ◽  
pp. 961-965 ◽  
Author(s):  
Berthold Kersting
Keyword(s):  
Single Crystal ◽  
Structure Analysis ◽  
Nickel Complex ◽  
Ring Size ◽  
X Ray ◽  
Large Ring ◽  
Square Planar ◽  
Distorted Octahedral ◽  
In Trans

AbstractThe syntheses and characterization of tetranuclear Ni complexes [(L2)Ni4][ClO4]4 (3) and [(L2)Ni4(NCS)4] (4) of a 40-membered macrocyclic octaamine-tetrathiophenolate ligand (L2)4- are described. Single-crystal X-ray structure analysis of 4 reveals well-separated molecules of the tetranuclear isothiocyanate complex [(L2) NiII4(NCS)4]. The four NiII centers are arranged in binuclear [N2Ni(μ2-SR)2NiN2(NCS)2] subunits containing distorted square-planar NiN2S2 and distorted octahedral NiN2S2(NCS)2 sites. The fact that the two isothiocyanate groups at the octahedral Ni site are in trans positions can be ascribed to the large ring size of the macrocycle

scholarly journals Darstellung und Reaktionen von zweikernigen Platin(II)-Komplexen; Einkristall-Röntgenstrukturanalyse eines Tetrakis(difluorphosphonato)-Palladat(II)-Komplexes / Preparation and Reactions of Binuclear Platinum(II) Complexes. Single Crystal X-Ray Diffraction Study of a Tetrakis(difluorophosphonato)palladate(II) Complex

1993 ◽  
Vol 48 (6) ◽  
pp. 737-746 ◽  
Author(s):  
Hans-Jürgen Plinta ◽  
Robert Gereke ◽  
Axel Fischer ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Diffraction Study ◽  
Mononuclear Complex ◽  
Chloro Complex ◽  
Addition Reactions ◽  
Silyl Ether ◽  
X Ray Diffraction ◽  
X Ray ◽  
Sulfuryl Fluoride ◽  
Square Planar ◽  
The Ideal

o-Methylbenzyldifluorophosphite 2 was obtained by the reaction of o-methylbenzyltrimethyl silyl ether 1 with chlorodifluorophosphine PF2Cl. The reaction of 2 with the palladium(II) complex 3 led to the tetrakis(difluorophosphonato)palladate(II) complex 7. The X-ray structure analysis of 7 confirmed the nearly exact square planar structure at the metal atom of the tetrakis(difluorophosphonato)palladate(II) dianion. Minimal deviations from the ideal geometry at palladium and phosphorus are mainly the result of thermal motion or disorder phenomena in the crystal. In the reaction of the platinum(II) complex 8 with chlorodifluorophosphine the binuclear tetrakis(chlorodifluorophosphine)platinum(II)chloro complex 9 was obtained. In acetonitrile, 9 was cleaved to form the mononuclear complex 10. Similar results were obtained in the oxidative addition reactions of the platinum(0) complex 11 with sulfuryl chloride fluoride, 12, sulfuryl fluoride, 13, and phosphorus pentafluoride. Tetrakis-(triphenylphosphine)-μ-dichlorodiplatinum(II) hexafluorophosphate 14 was isolated. In acetonitrile the mononuclear acetonitrile-bis(triphenylphosphine)chloroplatinum(II) hexafluorophosphate complex 15 was isolated.

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