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.

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 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.

scholarly journals Übergangsmetallkomplexe mit Schwefelliganden, CVIII+. Eine bequeme Synthese des tertiären Amin-thiolat-Liganden 'S2N2Me2'2-. Einfluß der Aminmethylierung auf die Koordinationschemie von Nickel- und Ruthenium-Komplexen mit [M('S2N2R2')]-Geriisten (R = H, CH3). ('S2N2Me2'2- = 1,2-Ethandiamin-N,N'-dimethyl-N,N'-bis(2-benzolthiolat)(2-)) / Transition Metal Complexes with Sulfur Ligands, CVIII+. A Facile Synthesis of the Tertiary Amine-thiolato Ligand 'S2N2Me2'2-. Influence of the Aminomethylation on the Coordination Chemistry of Nickel and Ruthenium Complexes with [M('S2N2R2')] Frameworks (R = H, CH3). ('S2N2Me2'2- = 1,2-Ethanediamino-N,N'-dimethyl-N,N'-bis(2-benzenethiolato)(2-))

1995 ◽  
Vol 50 (5) ◽  
pp. 791-801 ◽  
Author(s):  
Dieter Sellmann ◽  
Richard Ruf ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Coordination Chemistry ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Tertiary Amine ◽  
Spectroscopic Data ◽  
Benzyl Chloride ◽  
Spontaneous Resolution ◽  
Facile Synthesis ◽  
Consecutive Reaction ◽  
X Ray

Abstract In a single pot synthesis consecutive reaction of the tetradentate amine-thiole H2-'S2N2H2' 2 ('S2N2H2'2- = 1,2-ethanediamino-N,N'-bis(2-benzenethiolato)(2-)). with [LiN(SiMe3)2] and benzyl chloride (BzCl) yields the amine-thioether 'Bz2S2N2H2' which gives the tertiary amine-thioether 'Bz2S2N2Me2' when reacted with further [LiN(SiMe3)2] and CH3I Removal of the benzyl groups with an excess of sodium and acidification with hydrochloric acid finally yield H2-'S2N2Me2' I ('S2N2Me2'2- = 1,2-ethanediamino-N,N'-di- methyl-N,N'-bis(2-benzenethiolato)(2-)). 1 and 2 have been characterized by X-ray structure analysis. With [Ni(CH3COO)2] · 4H2O,1 yields racemic [Ni('S2N2Me2')] 3 in a diastereospecific reaction. Crystallization of 3 leads to spontaneous resolution of the racemate. By X-ray structure analysis of 3 the absolute configuration in the single crystal examined was determi­ned using Roger's μ-refinement (μ = 1.00(4)). Upon reaction with [RuCl3·3H2O]. LiOMe and CO. I yields [Ru(CO)2('S2N2Me2')] 5. Spectroscopic data indicate that 5 and the parent complex [Ru(CO)2('S2N2H2')] differ with respect to their core structures. Influence of the amine methylation on structure and reactivity of complexes with [M('S2N2R2')] cores, R = H. Me, is discussed.

Übergangsmetallkomplexe mit Schwefelliganden, LXXXVI. Säure-Base- und Redox-Reaktionen von [Ni(′MeS2′)2] mit H+, PMe3, NO+ und NO. Röntgenstrukturanalyse von [Ni(PMe3)(′MeS2′)2] (′MeS2′ = o-(Methylthio)thiophenolat(1–)) / Transition-Metal Complexes with Sulfur Ligands, LXXXVI. Acid-Base and Redox Reactions of [Ni(′MeS2')2] with H+, PMe3, NO+ and NO. X-Ray Structure Determination of [Ni(PMe3)(′MeS2′)2] (′MeS2′ = o-(methylthio)thiophenolate(1–))

1992 ◽  
Vol 47 (5) ◽  
pp. 748-754 ◽  
Author(s):  
Dieter Sellmann ◽  
Helmut Schillinger ◽  
Falk Knoch
Keyword(s):  
Transition Metal ◽  
Transition Metal Complexes ◽  
Structure Determination ◽  
Redox Reactions ◽  
Substitution Reactions ◽  
Acid Base ◽  
X Ray ◽  
Square Planar ◽  
Cis And Trans

In order to elucidate specific properties of nickel-sulfur complexes, addition and substitution reactions of [Ni(′MeS2′)2] (1) were investigated. 1 is rapidly hydrolyzed by aqueous HCl yielding ′MeS2′–H and Ni(II) ions. 1 coordinates phosphines as coligands, thioether donors decoordinate, however, simultaneously. The monophosphine complex [Ni(PMe3)(′MeS2′ )2] (2) was characterized by X-ray structure determination. It contains a square-planar NiS3P unit and one decoordinated thioether group. Redox reactions of 1 occur with NO+ and NO, yielding the binuclear nitrosyl complexes cis- and trans-[Ni(NO)(′MeS2′)]2 (3) and the disulfide [′MeS2']2•

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

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°

Übergangsmetallkomplexe mit Schwefelliganden, CI*. Synthese und Struktur von N2H5[Fe(N2H4)(S2C6H4)2] · 1,33N2H4 / Transition Metal Complexes with Sulfur Ligands, Cl*. Synthesis and Structure of N2H5[Fe(N2H4)(S2C6H4)2] · 1,33N2H4

1994 ◽  
Vol 49 (5) ◽  
pp. 660-664 ◽  
Author(s):  
Dieter Sellmann ◽  
Helge Friedrich ◽  
Falk Knoch
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
High Spin ◽  
Transition Metal Complexes ◽  
X Ray ◽  
Labile N

Attempts to coordinate N2H4 to [Fe(S2C6H4)2] fragments lead to N2H5[Fe(N2H4)(S2C6H4)2], which crystallizes from MeOH/N2H4 solutions as the solvate [(N2H5){Fe(N2H4)(S2C6H4)2} · 1,33 N2H4]. 1, and has been characterized by X-ray structure analysis. 1 contains three discrete N2H5+ cations, four N2H4 solvate molecules and three independent [Fe(N2H4)(S2C6H4)2]- anions which are connected via an extended network of N-H ··· N and N-H ··· S bridges. N2H5[Fe(N2H4)(S2ChH4)2] and 1 contain high-spin Fe(III) centers and labile N2H4 ligands.

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.

An X-Ray Structure Determination of the Twinned Crystals of Dinitrato-2,2′-dipyridylsilver(II)

1972 ◽  
Vol 50 (3) ◽  
pp. 315-323 ◽  
Author(s):  
G. W. Bushnell ◽  
M. A. Khan
Keyword(s):  
Silver Atom ◽  
Unit Cell ◽  
Planar Geometry ◽  
X Ray ◽  
Square Planar ◽  
Distorted Octahedral ◽  
Cell Dimensions ◽  
The Mean ◽  
Unit Cell Dimensions

The crystal structure of dinitrato-2,2′-dipyridylsilver(II) has been solved and refined to an R-value of 0.070. Four circle diffractometer measurements were obtained from the twinned triclinic crystals. The unit cell dimensions at 22 °C are: a = 697.5 ± 0.2 pm, b = 999.4 ± 0.2 pm, c = 1032.2 ± 0.2 pm, α = 113.46 ± 0.02°, β = 100.71 ± 0.02°, γ = 95.28 ± 0.02°. The space group is [Formula: see text] (No. 2) with two molecules per unit cell. The density is 2.06 ± 0.04 g cm−3 (measured), 2.02 g cm−3 (calculated). The four shortest bond lengths to silver are: Ag—O(1), 214.8 ± 1.5 pm; Ag—O(4), 213.6 ± 1.5 pm; Ag—N(1), 212.4 ± 1.6 pm; Ag—N(2), 220.7 ± 1.6 pm. These four bonds are distorted from square planar geometry with the silver atom lying 19.90 ± 0.17 pm out of the mean plane of the other four atoms. There are also long bonds to the nitrato groups of neighboring molecules: Ag—O(1′), 275.3 ± 1.3 pm; Ag—O(2″), 276.3 ± 1.6 pm. Inclusion of these bonds gives a distorted octahedral silver coordination. Though predominantly unidentate, there is a slight tendency toward bidentate bonding in both nitrato ligands: Ag—O(2), 305.8 ± 1.4 pm; Ag—O(5), 295.0 ± 1.7 pm. O(2) and O(5) approach the convex side of the distorted square planar coordination. The deviation from planarity of the closely bonded square, and angular distortions in the above mentioned octahedral coordination can be rationalized by considering the silver as eight coordinate. The bonds to silver may be grouped 4:2:2 by length or 4:3:1 by angular disposition.

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