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, 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.

New isostructural transition metal complexes with a non-innocent dithiolate ligand

2015 ◽  
Vol 71 (2) ◽  
pp. 159-164 ◽  
Author(s):  
Peter Herich ◽  
Marek Fronc ◽  
Jozef Kožíšek
Keyword(s):  
Transition Metal ◽  
Single Crystal ◽  
Transition Metal Complexes ◽  
Central Metal Atom ◽  
Central Metal ◽  
X Ray Diffraction ◽  
Interatomic Distances ◽  
Coordination Polyhedra ◽  
X Ray ◽  
Square Planar

Three new complexes with 3,6-dichlorobenzene-1,2-dithiol (bdtCl2), namely methyltriphenylphosphonium bis(3,6-dichlorobenzene-1,2-dithiolato-κ2S,S′)cobaltate(1−), (C19H18P)[Co(C6H2Cl2S2)2], (I), bis(methyltriphenylphosphonium) bis(3,6-dichlorobenzene-1,2-dithiolato-κ2S,S′)cuprate(2−) dimethyl sulfoxide disolvate, (C19H18P)2[Cu(C6H2Cl2S2)2]·2C2H6OS, (II), and methyltriphenylphosphonium bis(3,6-dichlorobenzene-1,2-dithiolato-κ2S,S′)cuprate(1−), (C19H18P)[Cu(C6H2Cl2S2)2], (III), have been synthesized and characterized by single-crystal X-ray diffraction. The X-ray structure analyses of all three complexes confirm that the four donor S atoms form a slightly distorted square-planar coordination arrangement around the central metal atom. An interesting finding for both the CuIIand CuIIIcomplexes,i.e.(II) and (III), respectively, is that the coordination polyhedra are principally the same and differ only slightly with respect to the interatomic distances.

Preparation, properties and structure of some intermediate nido- and arachno-monocarbaboranes

1981 ◽  
Vol 46 (10) ◽  
pp. 2345-2353 ◽  
Author(s):  
Karel Baše ◽  
Bohumil Štíbr ◽  
Jiří Dolanský ◽  
Josef Duben
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Nmr Spectra ◽  
Liquid Ammonia ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Starting Compound

The 6-N(CH3)3-6-CB9H11 carbaborane reacts with sodium in liquid ammonia with the formation of 6-CB9H12- which was used as a starting compound for preparing the 4-CB8H14, 9-L-6-CB9H13 (L = (CH3)2S, CH3CN and P(C6H5)3), 1-(η5-C5H5)-1,2-FeCB9H10-, and 2,3-(η5-C5H5)2-2,31-Co2CB9H10- carboranes. The 4-CB8H14 compound was dehydrogenated at 623 K to give 4-(7)-CB8H12 carborane. Base degradation of 6-N(CH3)3-6-CB9H11 in methanol resulted in the formation of 3,4-μ-N(CH3)3CH-B5H10. The structure of all compounds was proposed on the basis of their 11B and 1H NMR spectra and X-ray diffraction was used in the case of the transition metal complexes.

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.

Palladium Complexes with Bidentate P,N Ligands: Synthesis, Characterization and Application in Ethene Oligomerization

2002 ◽  
Vol 57 (7) ◽  
pp. 803-809 ◽  
Author(s):  
Gabi Müller ◽  
Martti Klinga ◽  
Peter Osswald ◽  
Markku Leskelä ◽  
Bernhard Rieger
Keyword(s):  
Single Crystal ◽  
Phosphorus Atom ◽  
Palladium Complexes ◽  
Metal Center ◽  
Coordination Geometry ◽  
Trans Position ◽  
Pyridine Ligand ◽  
X Ray ◽  
Square Planar ◽  
In Trans

Palladium complexes of two different P,N ligands (a phosphane-pyridine and a phosphane-imine ligand) were synthesized and characterized. Single crystal X-ray structure analyses of the palladium diiodide compounds revealed a square-planar coordination geometry at the metal center with a longer Pd-I bond in trans-position to the phosphorus atom. The chloro-methyl palladium species of the phosphane-pyridine ligand was applied for the oligomerization of ethene using a borate salt as cocatalyst.

scholarly journals New platinum(II) complexes with benzothiazole ligands

2016 ◽  
Vol 72 (3) ◽  
pp. 412-416 ◽  
Author(s):  
José A. Carmona-Negrón ◽  
Mayra E. Cádiz ◽  
Curtis E. Moore ◽  
Arnold L. Rheingold ◽  
Enrique Meléndez
Keyword(s):  
Single Crystal ◽  
Metal Atom ◽  
Cancer Chemotherapy ◽  
Potential Application ◽  
Dihedral Angles ◽  
Coordination Geometry ◽  
X Ray Diffraction ◽  
X Ray ◽  
Bond Lengths ◽  
Square Planar

Four new platinum(II) complexes, namely tetraethylammonium tribromido(2-methyl-1,3-benzothiazole-κN)platinate(II), [NEt4][PtBr3(C8H7NS)] (1), tetraethylammonium tribromido(6-methoxy-2-methyl-1,3-benzothiazole-κN)platinate(II), [NEt4][PtBr3(C9H9NOS)] (2), tetraethylammonium tribromido(2,5,6-trimethyl-1,3-benzothiazole-κN)platinate(II), [NEt4][PtBr3(C10H11NS)] (3), and tetraethylammonium tribromido(2-methyl-5-nitro-1,3-benzothiazole-κN)platinate(II), [NEt4][PtBr3(C8H6N2O2S)] (4), have been synthesized and structurally characterized by single-crystal X-ray diffraction techniques. These species are precursors of compounds with potential application in cancer chemotherapy. All four platinum(II) complexes adopt the expected square-planar coordination geometry, and the benzothiazole ligand is engaged in bonding to the metal atom through the imine N atom (Pt—N). The Pt—N bond lengths are normal: 2.035 (5), 2.025 (4), 2.027 (5) and 2.041 (4) Å for complexes1,2,3and4, respectively. The benzothiazole ligands are positioned out of the square plane, with dihedral angles ranging from 76.4 (4) to 88.1 (4)°. The NEt4cation in3is disordered with 0.57/0.43 occupancies.

Two ZnIImononuclear coordination compounds with pyridinedicarboxylate and auxiliaryN-(pyridin-4-ylmethylidene)hydroxylamine ligands

2014 ◽  
Vol 70 (12) ◽  
pp. 1101-1104 ◽  
Author(s):  
Eduard B. Coropceanu ◽  
Ana Dreab ◽  
Lilia Croitor
Keyword(s):  
Single Crystal ◽  
Coordination Compounds ◽  
Octahedral Geometry ◽  
Distorted Octahedral Geometry ◽  
Water Molecules ◽  
Coordination Geometry ◽  
X Ray ◽  
Trigonal Bipyramidal Coordination ◽  
Trigonal Bipyramidal ◽  
Distorted Octahedral

Two new mononuclear coordination compounds, bis{4-[(hydroxyimino)methyl]pyridinium} diaquabis(pyridine-2,5-dicarboxylato-κ2N,O2)zincate(II), (C6H7N2O)2[Zn(C7H3NO4)2(H2O)2], (1), and (pyridine-2,6-dicarboxylato-κ3O2,N,O6)bis[N-(pyridin-4-ylmethylidene-κN)hydroxylamine]zinc(II), [Zn(C7H3NO4)(C6H6N2O)2], (2), have been synthesized and characterized by single-crystal X-ray diffractometry. The centrosymmetric ZnIIcation in (1) is octahedrally coordinated by two chelating pyridine-2,5-dicarboxylate ligands and by two water molecules in a distorted octahedral geometry. In (2), the ZnIIcation is coordinated by a tridentate pyridine-2,6-dicarboxylate dianion and by twoN-(pyridin-4-ylmethylidene)hydroxylamine molecules in a distortedC2-symmetric trigonal bipyramidal coordination geometry.

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.

Transition Metal Complexes of Derivatized Chiral Dihydro-1,2,4-triazin-6-ones. Part III [1]. X-Ray Crystal Structure Analysis of N,N’-Bis[(1-phenyl-5-isopropyl-4,5-dihydro-6-oxo-1,2,4-triazin-3-yl)ethylidene]- propane-1,3-diamine Nickel(II)

2000 ◽  
Vol 55 (11) ◽  
pp. 1074-1078 ◽  
Author(s):  
Ahmad S. Abushamleh ◽  
Mustafa M. El-Abadelahb ◽  
Wolfgang Voelter
Keyword(s):  
Crystal Structure ◽  
Transition Metal ◽  
Transition Metal Complexes ◽  
Structure Determination ◽  
Nickel Complex ◽  
Crystal Structure Analysis ◽  
High Yield ◽  
X Ray ◽  
Square Planar ◽  
Template Reaction

Template reaction of L-3-acetyl-1-phenyl-5-isopropyl-4,5-dihydro-1,2,4-triazin-6-one (lb) with 1,3-diaminopropane and nickel acetate gave the corresponding chiral complex 4 in high yield. X-ray structure determination showed that the nickel complex is square planar, and the ligand N,N’-bis[(l-phenyl-5-isopropyl-4,5-dihydro-6-oxo-1,2,4-triazin-3-yl)ethylid-ene]- propane-1,3-diamine is of tetra-aza type where the imine nitrogens and the ring HN(4) nitrogens are the coordinating sites. MS-FAB and NMR spectral data are in agreement with the X-ray structure.

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