Aminkomplexe des Goldes, Teil 10: Gold(I)-thiocyanat-Komplexe mit Tetrahydrothiophen, Dimethylsulfid, Ammoniak, Aminen und Azaaromatena

2018 ◽  
Vol 73 (2) ◽  
pp. 125-147 ◽  
Author(s):  
Mark Strey ◽  
Cindy Döring ◽  
Peter G. Jones
Keyword(s):  
Dimethyl Sulfide ◽  
Crystal Packing ◽  
Molecular Structures ◽  
Secondary Amines ◽  
X Ray ◽  
Anions And Cations ◽  
Derivatives Of ◽  
Aurophilic Interactions ◽  
Ray Methods ◽  
Alternating Chain

AbstractThe reaction of (tht)AuCl (tht=tetrahydrothiophene) with KSCN leads to a mixture of gold(I) thiocyanate AuSCN and [(tht)2Au]+ [Au(SCN)2]−1. The compounds were separated and the X-ray structure of 1 confirmed as an alternating chain of anions and cations linked by aurophilic contacts. Either pure AuSCN or the mixture was used to synthesize further derivatives of AuSCN, all of which were investigated by X-ray methods. Most products were of limited stability when removed from their mother liquor. The dimethyl sulfide derivative 2 is molecular, (Me2S)AuSCN; the ammonia derivative 3 is ionic, [(NH3)2Au]+ [Au(SCN)2]−. The reaction with 2,2-bipyridyl leads (presumably by involvement of the solvent or of atmospheric moisture) to [bipy-H]+ [Au(SCN)2]−13. All other products involve amines or azaaromatics as ligands L. The primary amine tert-butylamine forms an ionic product [L2Au]+ (SCN)−4. The secondary amines piperidine and dibenzylamine lead to molecular structures LAuSCN (5 and 6), whereas pyridine-based azaaromatics lead to ionic products [L2Au]+ [Au(SCN)2]− with L=2-, 3- or 4-picoline (7–9), 2,4-, 3,4- or 3,5-lutidine (10–12). The 3,4-lutidine derivative 11 forms two polymorphs that tend to form mixed crystals. The dominant features of the crystal packing for 7–12 are short aurophilic interactions.

β-Hydroxydithiozimtsäurederivate als Liganden. Synthese und Charakterisierung neuartiger 1,1-Ethendithiolato- und O,S-Chelatkomplexe / Derivatives of β -Hydroxydithiocinnamic Acids as Ligands. Syntheses and Characterisation of Novel 1,1-Ethenedithiolato and O,S-Chelate Complexes

2007 ◽  
Vol 62 (3) ◽  
pp. 475-482 ◽  
Author(s):  
Karsten Schubert ◽  
Helmar Görls ◽  
Wolfgang Weigand
Keyword(s):  
Bidentate Ligand ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Chelate Complexes ◽  
X Ray ◽  
H Nmr ◽  
Hexyl Ester ◽  
Elemental Analyses ◽  
Derivatives Of ◽  
C Nmr

Starting from 4-bromoacetophenone 1, the 4-bromo-β -hydroxydithiocinnamic acid 2 and the 4-bromo-β -hydroxydithiocinnamic acid hexyl ester 3 were prepared using carbon disulfide and potassium-tert-butylate as a base. Acting as a ligand, the acid gives 1,1-ethenedithiolato complexes with (Ph3P)2Pt(II) (4a), (Et3P)2Pt(II) (4b), dppePt(II) (4c), (Ph3P)2Pd(II) (4d), dppePd(II) (4e), and dppeNi(II) (4f). In contrast to the acid, the deprotonated ester 3 forms a monoanionic bidentate ligand. [O,S] Complexes of Pt(II) (5a), Pd(II) (5b) and Ni(II) (5c) were obtained. All complexes have been fully characterised using 1H NMR, 13C NMR and 31P NMR spectroscopy, mass spectrometry, infrared spectroscopy and elemental analyses. The molecular structures of the complexes 4b and 5a - 5c were determined by X-ray diffraction analyses.

Übergangsmetallkomplexe mit Nitroxidradikalen: Palladium-, Platin-, Pentamethylcyclopentadienyl-rhodium- und -iridium-Komplexe sowie α-Aminocarboxylatkomplexe mit Donor-haltigen Derivaten des 2,5-Dihydroimidazol-l-oxyls / Transition Metal Complexes of Nitroxide Radicals, Palladium, Platinum, Pentamethylcyclopentadienyl Rhodium and Iridium Complexes, and α-Aminocarboxylate Complexes with Derivatives of 2,5-Dihydroimidazole-l-oxyls

1998 ◽  
Vol 53 (1) ◽  
pp. 101-109 ◽  
Author(s):  
Frank Hintermaier ◽  
Sylvia Helding ◽  
Leonid B. Volodarsky ◽  
Karlheinz Sünkel ◽  
Kurt Polbom ◽  
...  
Keyword(s):  
Nitrogen Atom ◽  
Molecular Structures ◽  
Iridium Complexes ◽  
X Ray Diffraction ◽  
Chelate Complexes ◽  
X Ray ◽  
Ring Nitrogen ◽  
Derivatives Of ◽  
Ring Nitrogen Atom ◽  
Palladium Platinum

2,5-Dihydroimidazoline-l-oxyl radicals I, II with imino substituents coordinate to Pd(II) and Pt(II) complexes with formation of the N,N chelate complexes 1-6. With oxygen containing substituents either monodentate N-coordination to give 8 or N ,O chelate formation to give 9 takes place, depending on the position of the oxygen atom relative to the ring nitrogen atom. With radicals III that also have the second ring nitrogen atom oxidized and the Rh(III) or Ir(III) complexes [Cp*MCl2]2 the O , O chelates 11 -13 could be obtained, while with Na2PdCl4 the heterocycle was destroyed with formation of a N,N chelate complex 10 of an α-nitrosooxime ligand. The orthopalladated 2,2,5,5 tetramethyl-4-phenyl-2,5-dihydroimidazoline-l-oxyl complex 7a reacts with several a-amino acidates under splitting of the dichloro bridge with formation of the C,N/N,O-bis-chelate complexes 7b-f. The molecular structures of 2 and 10 were determined by X-ray diffraction.

scholarly journals 2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties

2015 ◽  
Vol 11 ◽  
pp. 2179-2188 ◽  
Author(s):  
Yury A Sayapin ◽  
Inna O Tupaeva ◽  
Alexandra A Kolodina ◽  
Eugeny A Gusakov ◽  
Vitaly N Komissarov ◽  
...  
Keyword(s):  
Density Functional ◽  
Acetic Acid Solution ◽  
Intramolecular Proton Transfer ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Dft Methods ◽  
Functional Theory ◽  
X Ray ◽  
X Ray Crystallography ◽  
Derivatives Of

A series of derivatives of 2-hetaryl-1,3-tropolone (β-tropolone) was prepared by the acid-catalyzed reaction of 2-methylbenzoxazoles, 2-methylbenzothiazoles and 2,3,3-trimethylindoline with 3,4,5,6-tetrachloro-1,2-benzoquinone. The molecular structures of the three representative compounds were determined by X-ray crystallography. In crystal and (as shown by the DFT PBE0/6-311+G** calculations) in solution, 2-hetaryl-4,5,6,7-tetrachloro- and 2-hetaryl-5,6,7-trichloro-1,3-tropolones exist in the NH-tautomeric form with a strong resonance-assisted intramolecular N–H···O hydrogen bond. The mechanism of the formation of 1,3-tropolones in the reaction of methylene-active five-membered heterocycles with o-chloranil in acetic acid solution has been studied using density functional theory (DFT) methods. The reaction of 2-(2-benzoxa(thia)zolyl)-5,6,7-trichloro(4,5,6,7-tetrachloro)-1,3-tropolones with alcohols leads to the contraction of the seven-membered tropone ring with the formation of 2-(2-benzoxa(thia)zolyl)-6-alkoxycarbonylphenols. The molecular structure of 2-(2-ethoxycarbonyl-6-hydroxy-3,4,5-trichlorophenyl)benzoxazole has been determined by X-ray diffraction. 2-(2-Benzoxa(thia)zolyl)-6-alkoxycarbonylphenols display intense green fluorescence with anomalous Stokes shifts caused by the excited state intramolecular proton transfer (ESIPT) effects.

scholarly journals Molecular Structures Polymorphism the Role of F…F Interactions in Crystal Packing of Fluorinated Tosylates

Crystals ◽  
2019 ◽  
Vol 9 (5) ◽  
pp. 242 ◽  
Author(s):  
Dmitry E. Arkhipov ◽  
Alexander V. Lyubeshkin ◽  
Alexander D. Volodin ◽  
Alexander A. Korlyukov
Keyword(s):  
Intermolecular Interactions ◽  
Crystal Packing ◽  
Lattice Energy ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Total Contribution ◽  
X Ray ◽  
Weak Hydrogen Bonds ◽  
Intermolecular Bonding

The peculiarities of interatomic interactions formed by fluorine atoms were studied in four tosylate derivatives p-CH3C6H4OSO2CH2CF2CF3 and p-CH3C6H4OSO2CH2(CF2)nCHF2 (n = 1, 5, 7) using X-ray diffraction and quantum chemical calculations. Compounds p-CH3C6H4OSO2CH2(CF2)nCHF2 (n = 1, 5) were crystallized in several polymorph modifications. Analysis of intermolecular bonding was carried out using QTAIM approach and energy partitioning. All compounds are characterized by crystal packing of similar type and the contribution of intermolecular interactions formed by fluorine atoms to lattice energy is raised along with the increase of their amount. The energy of intra- and intermolecular F…F interactions is varied in range 0.5–13.0 kJ/mol. Total contribution of F…F interactions to lattice energy does not exceed 40%. Crystal structures of studied compounds are stabilized mainly by C-H…O and C-H…F weak hydrogen bonds. The analysis of intermolecular interactions and lattice energies in polymorphs of p-CH3C6H4OSO2CH2(CF2)nCHF2 (n = 1, 5) has shown that most stabilized are characterized by the least contribution of F…F interactions.

Synthesis, Characterization, and Chemistry of Dimethyl Sulfide Derivatives of closo-B10H102-

2002 ◽  
Vol 67 (7) ◽  
pp. 1007-1024 ◽  
Author(s):  
Heather D. Hall ◽  
Bradley D. Ulrich ◽  
Roman G. Kultyshev ◽  
Jianping Liu ◽  
Shengming Liu ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Single Crystal ◽  
Diffraction Analysis ◽  
Liquid Ammonia ◽  
Dimethyl Sulfide ◽  
X Ray Diffraction ◽  
Chiral Column ◽  
X Ray ◽  
Derivatives Of

The reaction of Cs2[B10H10] with DMSO in acid produces the disubstituted 1,10-, 1,6-, and 2,7(8)-isomers of (Me2S)2B10H8 as well as the monosubstituted [(Me2S)B10H9]- anion. Through a modified procedure, the trisubstituted compound 1,10-(Me2S)2-2-(MeS)B10H7 was prepared and characterized. The 1,10-(Me2S)2B10H8 isomer was converted to the enantiomers 2,7-(Me2S)2B10H8 and 2,8-(Me2S)2B10H8 which were separated on a chiral column. The 1,6-(Me2S)2B10H8 isomer was converted to a mixture of 1,10-(Me2S)2B10H8 and 2,3-(Me2S)2B10H8. These polyhedral rearrangements are believed to occur through the diamond-square-diamond mechanism. The 1,6- and 1,10-(Me2S)2B10H8 isomers were reduced with alkali metal in liquid ammonia to produce the dianions [1,6-(MeS)2B10H8]2- and [1,10-(MeS)2B10H8]2-, respectively. Sodium ethanethiolate was used for the reduction of [1-(Me2S)B10H9]- and 1,10-(Me2S)2B10H8 to form [1-(MeS)B10H9]2- and [1-(MeS)-10-(Me2S)B10H8]-, respectively. The structures of 1,10-(Me2S)2B10H8, 1,6-(Me2S)2B10H8, 2,8-(Me2S)2B10H8, 2,3-(Me2S)2B10H8, 1,10-(Me2S)2-2-(MeS)B10H7, [1-(MeS)-10-(Me2S)B10H8]-, and [1,6-(MeS)2B10H8]2- were determined by single-crystal X-ray diffraction analysis.

Sign in / Sign up

Export Citation Format

Share Document