Photoreaktionen von Dekacarbonyldirhenium mit Allen und unverzweigten Allenderivaten / Photoreactions of Decacarbonyldirhenium with Allene and Unbranched Derivatives of Allene

1995 ◽  
Vol 50 (4) ◽  
pp. 649-660 ◽  
Author(s):  
Cornelius G. Kreiter ◽  
Wolfgang Michels ◽  
Gerhard Heeb
Keyword(s):  
Nmr Spectra ◽  
Crystal And Molecular Structure ◽  
Reaction Products ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Oxidative Rearrangement ◽  
Dirhenium Complexes ◽  
Derivatives Of ◽  
By Products

Decacarbonyldirhenium (1) reacts upon UV irradiation with allene (2), 1,2-butadiene (3) and 2,3-pentadiene (4) preferentially by CO substitution and oxidative rearrangement to the corresponding enneacarbonyl-μ-η1:3-endiyl-dirhenium complexes 5, 9, and 15 and to the octacarbonyl-μ-η2:2-allene-dirhenium complexes 6, the stereoisomers 10, 11, and 16. At elevated temperature 5, 9, and 15 loose CO and yield by a reductive rearrangement also the complexes 6, 10, 11, and 16. In addition to these main products, depending upon the allene derivative used, various by-products are obtained.By-products of the reaction o f 1 with 2 are octacarbonyl-μ-η3:3-(2,3-dimethylene-buta-1,4- diyl)dirhenium (7) and μ-η2:2-allene-hexacarbonyl-μ-η1:3-1-propene-1,3-diyl-dirheniurn (8). The photo reaction of 1 with 3 yields, in addition to 9-11, tetracarbonyl-η3-(E-5-ethylidene- 4-methyl-2-cyclopenten-1-yl)rhenium (12) and tetracarbonyl-η3-(Z-5-ethyliden-4- methyl-2-cyclopenten-1-yl)rhenium (13) as a mixture of isomers. 1 and 4 form the by-products tetracarbonyl-η3-(EZ-3-penten-2-yl)rhenium (17), tetracarbonyl-η3-(EE-3-penten-2-yl)rhenium (18) and heptacarbonyl-μ-η1:2:1:2-(4,5-dimethyl-2,6-octadiene-3,6-diyl)dirhenium (19) with an unusually bridging and chelating ligand. The constitutions of the reaction products have been concluded from the IR and 1H NMR spectra. For 19 the crystal and molecular structure has been determined by X-ray diffraction analysis.

Derivatives of the Triaminoguanidinium Ion, 2. Prototropic Tautomerism, Crystal and Molecular Structure of N,N´,N´´-Tris(propan- 2-iminyl)guanidine [1, 2]

2013 ◽  
Vol 68 (3) ◽  
pp. 207-213 ◽  
Author(s):  
Jan Szabo ◽  
Gerhard Maas
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Prototropic Tautomerism ◽  
X Ray Diffraction ◽  
Temperature Dependent ◽  
X Ray ◽  
H Nmr ◽  
Compound C ◽  
Crystallographic Symmetry ◽  
Derivatives Of

The title compound, C10H20N6 (2), was prepared from N,N´,N´´-triaminoguanidinium chloride. Solvent- and temperature-dependent 1H NMR spectra indicating prototropic tautomerism were observed in solution. The crystal and molecular structure was determined by X-ray diffraction analysis. The compound crystallizes in the hexagonal space group P63/m. The molecules lie on crystallographic mirror planes parallel to the a,b plane, which are separated from each other by 3:37 Å . The threefold crystallographic symmetry of the molecules is due to disorder with positional averaging of individual molecules.

Reaktionsprodukte yon Oxylsäuremethylester-N-methylamiden mit Antimon(V)-chlorid. Molekülspektren und Struktur / Reaction Products of Oxalic Acid Methylester-N-methylamides and Antimony(V) Chloride. Molecular Spectra and Structure

1979 ◽  
Vol 34 (3) ◽  
pp. 398-405 ◽  
Author(s):  
M. Rössler ◽  
W. Schwarz ◽  
A. Schmidt
Keyword(s):  
Molecular Structure ◽  
Oxalic Acid ◽  
Nmr Spectra ◽  
Crystal And Molecular Structure ◽  
Molecular Spectra ◽  
Reaction Products ◽  
Addition Compound ◽  
Ring Systems ◽  
X Ray ◽  
H Nmr

Abstract Oxalic acid dimethylester and the oxalic acid methylester-N-methylamides 2 and 4, resp., react with antimony(V) chloride to yield the 1 : 1 addition compound 5 or the cyclic tetrachloroantimony(V) compounds 1, 3 and 6, resp., which represent SbO2C2 and SbONC2 five ring systems, resp. Li oxalic acid methylester-N-methylimide (9) and anti-mony(V) chloride gives the bicyclic octachloro-N-methylamido oxalato-O,O′-O,N-diantimony(V) (10). The crystal and molecular structure of tetrachloro-N-methylamino oxalato-O,O′-antimony(V) (3) is determined by X-ray analysis. The vibrational and 1H NMR spectra of 2-10 are reported and discussed.

scholarly journals Synthesis and X-ray diffraction of derivatives 2,4-dimethyl-6-oxo-1,6-dihydropyridin-3-carboxamide

2019 ◽  
Vol 60 (10) ◽  
pp. 1-23
Author(s):  
Ekaterina M. Feklicheva (Okul) ◽  
◽  
Victor B. Rybakov ◽  
Evgeny V. Babaev ◽  
Evgeny N. Ofitserov ◽  
...  
Keyword(s):  
Nmr Spectra ◽  
Synthesis Methods ◽  
X Ray Diffraction ◽  
Single Crystal Diffraction ◽  
Torsion Angles ◽  
X Ray ◽  
Nitrogenous Base ◽  
Derivatives Of ◽  
By Products ◽  
Chloride Monohydrate

Based on the synthesized starting 2,4-dimethyl-6-oxo-1,6-dihydropyridin-3-carboxamide crystallizing as a dihydrate, 9 derivatives of it including O- and N-phenacyl substituted products were obtained through original rearrangements and cyclizations. The corresponding oxazolopyridinium perchlorate was obtained from the latter preparation in the presence of acid, from which indolysin was obtained under the action of a nitrogenous base. The obtained molecular and crystal structures of all the compounds were studied by single crystal diffraction: 2,4-dimethyl-6-oxo-1,6-dihydropyridine-3-carboxamide dihydrate, 6-hydroxy-2,4-dimethyl-3-carbamoyl-pyridinium chloride monohydrate, 2,4-dimethyl-6-methoxypyridine-3-carboxamide, 1-[2-(4-methylphenyl)-2-oxoethyl]-2,4-dimethyl-6-oxo-1,6-dihydropyridine-3-carboxamide, 2,4-dimethyl-6-oxo-1-[2- (4-[chlorophenyl)-2-oxoethyl]-1,6-dihydropyridine-3-carboxamide, 2,4-dimethyl-6-[2-(4-methylphenyl)-2-oxo-ethoxy]pyridin-3-carbox-amide, 2,4-dimethyl-6-[2-(4-chlorophenyl)-2-oxoethoxy] pyridin-3-carb xamide, 6-carbamoyl-2-(4-chlorophenyl)-5,7-dimethyl[1,3]oxazolo[3,2-a]pyridin-4 perchlorate, 7-methyl-5-morpholin-4 -yl-2-(4-chlorophenyl) indolysin-8-carboxamide. A structural analysis of the by-products of 1,4-bis (4-methylphenyl) butane-1,4-dione and 1,4-bis(4-chlorophenyl) butane-1,4-dione was also carried out. The synthesis methods of each of them are given. A comparative analysis of bond lengths, valence and torsion angles in similar fragments of molecules is carried out. Hydrogen bonds were revealed in the structures and their influence on the strength of molecular packing in crystals was shown. All structures of the studied compounds, in addition to XRD, are characterized by 1H NMR spectra.

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.

Organometallic oxides: preparation of the cluster [(η-C5Me5)Mo]4O7 by reduction of [(η-C5Me5)MoCl(O)]2(μ-O) or (η-C5Me5)MoCl2(O)

2000 ◽  
Vol 78 (3) ◽  
pp. 383-394
Author(s):  
Frank Bottomley ◽  
Victor Sanchez ◽  
Robert C Thompson ◽  
Olusola O Womiloju ◽  
Zhiqiang Xu
Keyword(s):  
Nmr Spectra ◽  
Chloroform Solution ◽  
X Ray Diffraction ◽  
Broad Resonance ◽  
Nmr Spectrum ◽  
X Ray ◽  
Temperature Range ◽  
H Nmr ◽  
Tributyltin Hydride ◽  
Effective Moment

Reduction of [(η-C5Me5)MoCl(O)]2(μ-O) or (η-C5Me5)MoCl2(O) with sodium or magnesium amalgam, magnesium turnings, or tributyltin hydride produced [(η-C5Me5)Mo]4O7, with [(η-C5Me5)Mo(O)(μ-O)]2 as a co-product. [(η-C5Me5)Mo]4O7 was characterized by X-ray diffraction, mass spectrometry, 1H NMR and IR spectroscopies, and magnetism. Crystals of [(η-C5Me5)Mo]4O7 contained a tetrahedral [(η-C5Me5)Mo]4 unit (Mo-Mo = 2.909 (3) Å) with the Mo4O7 core having the structure Mo4(μ2-O(b))3(µ2-O(c))3(µ3-O(a)) (3). Microcrystalline samples of [(η-C5Me5)Mo]4O7 were paramagnetic over the temperature range 2-300 K, with an effective moment of 1.26 μB at 300 K. [(η-C5Me5)Mo]4O7 was also paramagnetic in chloroform solution, over the temperature range 223-298 K, with an effective moment of 1.43 µB at 298 K. The 1H NMR spectrum showed a broad resonance at 16.3 ppm (Δν 1/2 = 113 Hz) and two narrow resonances at 1.89 ppm and 1.69 ppm (Δν 1/2 = 5 Hz). The magnetism and NMR spectra showed that [(η-C5Me5)Mo]4O7 existed in two forms which were in equilibrium in solution. One form was paramagnetic (S = 1), with the Mo4O7 core having the geometry 3, and the other was diamagnetic (S = 0), with the Mo4O7 core having the geometry 4.Key words: cluster, cyclopentadienyl, molybdenum, oxide, paramagnetism.

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.

Darstellung, 11B-, 13C-NMR- und Schwingungsspektren von Cs2[B6H5(p-C6H4(NO2))] und Cs2[B6H5(C6H3-l-(CH3)-5-(NO2))] sowie Kristallstruktur von (CH2Py2)[B6Cl5(p-C6H4(NO2))]·CH3CN / Preparation, 11B , 13C-NMR and Vibrational Spectra of Cs2[B6H5(p-C6H4(NO2))], Cs2[B6H5 (C6H3-1 -(CH3 )-5-(NO2))] and Crystal Structure of (CH2Py2)[B6Cl5(p-C6H4(NO2))]·CH3CN

2000 ◽  
Vol 55 (11) ◽  
pp. 1031-1036
Author(s):  
S. Zander ◽  
W. Preetz
Keyword(s):  
13C Nmr ◽  
Nmr Spectra ◽  
Deae Cellulose ◽  
Ion Exchange Chromatography ◽  
Exchange Chromatography ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
X Ray ◽  
Derivatives Of ◽  
Ir And Raman

The first aryl derivatives of c/oso-hexahydrohexaborate are formed by reaction of [B6H6]2- with 1-bromo-4-nitrobenzene and 2-bromo-5-nitrotoluene in acetonitrile at 80 °C. Cs2[B6H5- (1,4-C6H4(NO2))] and Cs2[B6H5(C6H3-1-(CH3)-5-(NO2))] can be isolated by ion exchange chromatography on diethylaminoethyl (DEAE) cellulose. Further treatment with /V-chlorosuccinimide yields the perhalogenated derivative (CH2Py2)[B6Cl5(1,4-Ph(NO2))]CH3CN which has been characterized by X-ray diffraction analysis (orthorhombic, space group P2( 2,2t, a = 9.810(4), b - 14.412(3), c - 18.586(9) A, Z = 4). The 11B NMR spectra of all compounds are consistent with a monosubstituted B6-cluster. The IR and Raman spectra exhibit characteristic BB, BH, CH, CC and NO vibrations, respectively.

Synthesis and Electrochemistry of Aluminum Porphycenes: Crystal and Molecular Structure of Methyl-σ-Bonded Aluminum Etioporphycene

1997 ◽  
Vol 01 (02) ◽  
pp. 109-119 ◽  
Author(s):  
ROGER GUILARD ◽  
VIRGINIE PICHON-PESME ◽  
HASSANE LACHEKAR ◽  
CLAUDE LECOMTE ◽  
ALLY M. AUKAULOO ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Structural Data ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Axial Ligands ◽  
Uv Visible

The synthesis and characterization of three monomeric aluminum porphycenes with anionic or σ-bonded axial ligands is reported. The investigated compounds are represented as ( EtioPc ) Al ( CH 3) and ( EtioPc ) AlX where EtioPc represents the dianion of etioporphycene and X = Cl − or OH −. Each synthesized complex was characterized by mass spectrometry. 1 H NMR, IR and UV-visible spectroscopies as well as by electrochemistry. Comparisons are made between the properties of complexes in the aluminum etioporphycene series and related chloro- or methyl σ-bonded Al ( III ) porphyrins containing octaethylporphyrin ( OEP ) or tetraphenylporphyrin ( TPP ) macrocycles. Comparisons are also made between the currently investigated compounds and a previously reported Al ( III ) μ-oxo dimer, [( EtioPc ) Al ]2 O . In addition, the crystal and molecular structure of ( EtioPc ) Al ( CH 3) was determined by X-ray diffraction. The molecular structure of this methyl-σ-bonded aluminum etioporphycene provides the first structural data for an aluminum porphycene compound. The aluminum(III) atom in ( EtioPc ) Al ( CH 3) is pentacoordinated and is located 0.54 Å from the plane of the four N -nitrogens.

On the Stereoselectivity of the (-)-Dimenthyl Malonate Addition to α,β-Unsaturated Ketones

1996 ◽  
Vol 61 (12) ◽  
pp. 1805-1814 ◽  
Author(s):  
Ľubomír Šebo ◽  
Juraj Alföldi ◽  
Grety Rihs ◽  
Štefan Toma
Keyword(s):  
Michael Addition ◽  
Pure State ◽  
Nmr Spectra ◽  
Reaction Products ◽  
X Ray ◽  
Unsaturated Ketones ◽  
H Nmr ◽  
The Michael Addition

The Michael addition of (-)-dimenthyl malonate to eight α,β-unsaturated ketones has been studied. The ratio of diastereomers was calculated on the basis of the 1H NMR spectra of the crude reaction products. The diastereomer excess varied from 10 to 50%, depending on the structure of the starting enone. The pure diastereomer produced by addition of (-)-dimenthyl malonate to 2-benzylidene-1,4-indandione was isolated by repeated crystallization. X-ray analysis has shown that the isomer is (-)-dimenthyl (R)-2-[1-(1,3-dioxoindan-2-yl)-1-phenylmethyl]malonate (5a). The predominating diastereomers of (-)-dimenthyl(3-ferrocenyl-3-oxophenylpropyl)malonate (1a) and (-)-dimenthyl-2-(1-(1,3-dioxo[3]ferrocenophan-2-yl)-1-phenyl malonate (6a) were also isolated in pure state by careful crystallization.

Preparation and Crystal Structure of Genistein Benzenesulfonate Prodrugs

2008 ◽  
Vol 2008 (10) ◽  
pp. 555-558 ◽  
Author(s):  
You Peng ◽  
Zeyuan Deng ◽  
Shaojie Lang ◽  
Yawei Fan
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Sulfonic Acid ◽  
Nmr Spectra ◽  
High Yield ◽  
X Ray Diffraction ◽  
Aromatic Rings ◽  
X Ray ◽  
H Nmr ◽  
Ester Prodrugs

In order to improve bioavailability and anticancer activity of genistein, a series of novel sulfonic acid ester prodrugs of the isoflavone genistein were synthesised in high yield with excellent regioselectivity. Their structures were characterised by IR, MS, elemental analysis and 1H NMR spectra. The crystal structure was examined by X-ray diffraction. X-ray structure determination revealed that all the aromatic rings in the compound are not coplanar. In the crystal structure, molecules are linked through intermolecular C-H···O hydrogen bonds, forming layers parallel to the ab plane.

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