η3-Allylmeta]l-Schwefel-Komplexe, VI. Anionische η3-Allylnickel- und -palladium-Schwefel-Cluster/ η3-Allylmetal-Sulfur-Complexes, VI. Anionic η3-Allylnickel- and -palladium-Sulfur-Clusters

1983 ◽  
Vol 38 (5) ◽  
pp. 604-610 ◽  
Author(s):  
Reinhard Benn ◽  
Borislav Bogdanović ◽  
Peter Göttsch ◽  
Martin Rubach
Keyword(s):  
Crystal Structure ◽  
Nmr Spectra ◽  
Ionic Structure ◽  
Butyl Lithium ◽  
Sulfur Cluster ◽  
Anionic Clusters ◽  
H Nmr ◽  
Trigonal Bipyramidal ◽  
Lithium Sulfide

Abstractη3-Allylhydrogensulfidonickel (2) reacts with n-butyllithium with elimination of lithium sulfide and formation of the ionic η3-allylnickel-sulfur-cluster [(η3-C3H5Ni)3S2]+[Li(THF)2]- (4). The crystal structure of the analogous THF-TMEDA-adduct (4′) indicates that the nickel and sulfur atoms of the anion adopt a trigonal bipyramidal arrangement, in which the sulfur atoms are at the apices of the bipyramid. The Li(THF)2+ cation in 4 can be replaced by the (n-C4H9)4N+ cation (5). The 1H NMR spectra suggest the presence of two stereoisomers of the anionic clusters in 4 and 5 having C3h and Cs symmetry. In the reaction of η3-allyl- or η3-methallylhydrogensulfidopalladium (6, 6 a) with n-butyl-lithium crystalline compounds having the composition RC3H4PdSLi(THF)≈4, R = H, CH3 (7, 7 a) are obtained; their 1H NMR spectra also reveal the existence of the two stereoisomers having C3h and Cs symmetry. The same type of stereoisomerism is observed with the crystalline [(n-C4H9)4N]+[(η3-C3H5Pd)3S2]- (8) obtained from 7 and (n-C4H9)4N+ClO4-. For 7 and 7 a an ionic structure consisting of trigonal bipyramidal (η3-RC3H4Pd)3S2- anions and Li3S(THF)4+ cations is proposed.

Das 7,8-Benzo-5-chloro-1,4,4-trimethyl-1-aza-4-azonia-6,9-dioxa-5 λ5-phosphaspiro[4.4]nonanyl-Kation: Röntgenstrukturanalyse und temperaturabhängige 1H-NMR-Spektren: The 7, 8-Benzo-5-chloro-1,4,4-trimethyl-1-aza-4-azonia-6,9-dioxa-5 λ).5-phosphaspiro[4.4]nonanyl Cation: X-Ray Crystal Structure Determination and Variable 1H NMR Spectra

1992 ◽  
Vol 47 (6) ◽  
pp. 755-759 ◽  
Author(s):  
Thomas Kaukorat ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Crystal Structure ◽  
1H Nmr ◽  
Nmr Spectra ◽  
Crystal Structure Analysis ◽  
Acceptor Interaction ◽  
Nmr Spectrum ◽  
X Ray ◽  
H Nmr ◽  
Trigonal Bipyramidal ◽  
Donor Acceptor

The 1H NMR spectrum of the spirophosphorane 3 at room temperature indicates dynamic behaviour of the cation. The low-temperature 1H NMR spectra of 3 exhibit two sets of doublets for the protons of the diastereotopic N(CH3)2 groups. The free enthalpy of activation for the dynamic process was determined (58.6 KJ/mole). In the reaction of 3 with sodium tetraphenylborate the crystalline compound, 4, involving the non-coordinating anion, [B(C6H5)4]-, was obtained. The X-ray crystal structure analysis of 4 reveals the presence of a five-membered ring, formally as a result of intramolecular donor-acceptor interaction between the nitrogen atom of the N(CH3)2 group and phosphorus. The geometry at phosphorus deviates somewhat from ideal trigonal bipyramidal.

Synthesis, Spectroscopic Properties, and Crystal Structure of the Oxonium Acid [H(OEt2)2]+[Ti2Cl9]–

2003 ◽  
Vol 58 (8) ◽  
pp. 745-750 ◽  
Author(s):  
Stefan Rannabauer ◽  
Tassilo Habereder ◽  
Heinrich Nöth ◽  
Wolfgang Schnick
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Single Crystals ◽  
Nmr Spectra ◽  
Spectroscopic Properties ◽  
Partial Hydrolysis ◽  
Distorted Tetrahedron ◽  
Methyl Carbon ◽  
H Nmr ◽  
The Stability

The oxonium acid [H(OEt2)2]+[Ti2Cl9]− (1) was obtained by the reaction of TiCl4 with Et2O in n-pentane and subsequent partial hydrolysis. Suitable single crystals of 1 were obtained by sublimation at 5° C ([H(OEt2)2]+[Ti2Cl9]−, P212121 (no. 19), Z = 4, a = 1101.08(8), b = 1328.4(2), c = 1525.0(2) pm, T = 193(2) K, 4489 independent reflections, 197 parameters, R1 = 0.049). The cation is made up from two independent Et2O molecules and one disordered proton on two split positions. Both ether molecules exhibit a W form, and their molecular planes include an angle of 74.1(7)°. Thus a distorted tetrahedron is formed by the four methyl carbon atoms of the two ether molecules. The distance O···O amounts to 237.7(1) pm. The proton of the cation was characterized both by 1H NMR (CDCl3, T = 23 °C: δ = 11.7 ppm, w1/2 = 100 Hz) and IR spectroscopy (3120 cm−1, ν vbr). The [Ti2Cl9]− ion consists of two face sharing octahedra. 47Ti and 49Ti NMR spectra were recorded in solution (CH2Cl2, T = 23 °C: δ 49Ti = 137 ppm, w1/2 = 175 Hz; δ 47Ti = −124 ppm, w1/2 = 250 Hz). The absence of a signal for TiCl4 at δ 49Ti = 0 ppm indicates the stability of the dinuclear anion in solution.

Zum ambidenten Charakter des Cyanotrihydroborat-Liganden in Uran(IV)-Organylen / On the Ambident Nature of the Cyanotrihydroborate Ligand in Organouranium(IV) Complexes

1983 ◽  
Vol 38 (11) ◽  
pp. 1369-1374 ◽  
Author(s):  
R. Dieter Fischer ◽  
Kenan Yünlü
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Colour Change ◽  
Metal Coordination ◽  
Temperature Dependent ◽  
H Nmr ◽  
Trigonal Bipyramidal ◽  
Oligomeric Complex

Both the acceptedly oligomeric complex [(C5H5)3U(μ-NCBH3)]n (1) and its hitherto unknown, appreciably more soluble and volatile homologue, [(CH3C5H4)3U(μ-NCBH3)]n (2), display NIR/VIS spectra typical of trigonal bipyramidal (tbp) metal coordination in the solid state, but of pseudotetrahedral (ψ-Td) coordination e.g. in CH2CI2 and C6H5CH3 solution. The 1H NMR spectra of 2 in these non coordinating solvents can be best explained in terms of temperature dependent equilibria involving the two rapidly interconverting ψ-Td-isomers (CH3C5H4)3U(η3-H3BCN) and (CH3C5H4)3UNCBH3. A reversible colour change: green ⇋ brown at 130-150 °C also suggests the facile rupture of U-H and U-N bonds, respectively, in thermally excited, polycrystalline (2).

Phosphinsubstituierte Chelatliganden, XIV [1]. Wasserstoff-Brückenbindung in THF-Addukten von Tetracarbonylchrom-und -molybdänkomplexen mit P,S-koordinierten Phosphinothioformamid-Liganden. Kristallstruktur von [(CO)4Cr(PPh2C(S)NHMe)] · THF Phosphine-Substituted Chelate Ligands, XIV [1]. Hydrogen Bonding in THF-Adducts of Tetracarbonylchromium and -molybdenum Complexes with P,S-Coordinated Phosphinothioformamide Ligands. Crystal Structure of [(CO)4Cr(PPh2C(S)NHMe)] · THF

1985 ◽  
Vol 40 (4) ◽  
pp. 512-517 ◽  
Author(s):  
Udo Kunze ◽  
Hussain Jawad ◽  
Wolfgang Hiller ◽  
Regina Naumer
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Nmr Spectra ◽  
Chelate Complexes ◽  
Triclinic Space Group ◽  
Lattice Constants ◽  
H Nmr ◽  
Contact Distance ◽  
Metal Hexacarbonyls

The tetracarbonyl chromium and molybdenum P,S-chelate complexes 1a, b and 2a, b are obtained by low-temperature photolysis of the metal hexacarbonyls with the neutral phosphinothioformamide ligands, Ph2PC(S)NHR (R = Me (a). Ph (b)), as stoichiometric 1/1 IHF adducts. A weak N-H···O(THF) hydrogen bond is deduced from the 1H NMR spectra which show a collapse of the N-methyl doublet in la (Tc -18 °C) but not in 2a. Unusually small P-C(S) couplings are observed in the 13C{1H} NMR spectra. The N-methyl chromium complex la crystal­lizes in the triclinic space group P1 (Z = 2) with the lattice constants a = 1076.6(3), b = 1235.8(3), c = 915.1(3) pm, α = 97.99(4)°, β = 92.73(5)°, γ = 87.63(5)°. The planar thioamide unit adopts the Z configuration and is linked to the tetrahydrofuran molecule by a hydrogen bond (N-H1-O31 164°) with an O···H contact distance of 191 pm.

scholarly journals Crystal structure and solvent-dependent behaviours of 3-amino-1,6-diethyl-2,5,7-trimethyl-4,4-diphenyl-3a,4a-diaza-4-bora-s-indacene

2017 ◽  
Vol 73 (3) ◽  
pp. 378-382
Author(s):  
Lijing Yang ◽  
Brett Drew ◽  
Ravi Shekar Yalagala ◽  
Rameez Chaviwala ◽  
Razvan Simionescu ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Fluorescence Spectroscopy ◽  
Title Compound ◽  
Nmr Spectra ◽  
Membered Ring ◽  
The Other ◽  
Time Dependent ◽  
H Nmr ◽  
The Mean ◽  
Over Time

In the title compound (3-amino-4,4-diphenyl-BODIPY), C28H32BN3, the central six-membered ring has a flattened sofa conformation, with one of the N atoms deviating by 0.142 (4) Å from the mean plane of the other five atoms, which have an r.m.s. deviation of 0.015 Å. The dihedral angle between the two essentially planar outer five-membered rings is 8.0 (2)°. In the crystal, molecules are linkedviaweak N—H...π interactions, forming chains along [010]. The compound displays solvent-dependent behaviours in both NMR and fluorescence spectroscopy. In the1H NMR spectra, the aliphatic resonance signals virtually coalesce in solvents such as chloroform, dichloromethane and dibromoethane; however, they are fully resolved in solvents such as dimethyl sulfoxide (DMSO), methanol and toluene. The excitation and fluorescence intensities in chloroform decreased significantly over time, while in DMSO the decrease is not so profound. In toluene, the excitation and fluorescent intensities are not time-dependent. This behaviour is presumably attributed to the assembly of 3-amino-4,4-diphenyl-BODIPY in solution that leads to the formation of noncovalent structures, while in polar or aromatic solvents, the formation of these assemblies is disrupted, leading to resolution of signals in the NMR spectra.

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.

Dimeric aggregates of five-coordinated methyl(phthalocyaninato)Rh(III): 1H NMR evidence for staggered and slipped cofacial dimers

2001 ◽  
Vol 05 (06) ◽  
pp. 528-536 ◽  
Author(s):  
M. J. CHEN ◽  
J. W. RATHKE
Keyword(s):  
Crystal Structure ◽  
1H Nmr ◽  
Nmr Spectra ◽  
Solution Conformation ◽  
H Nmr ◽  
Phthalocyanine Complex ◽  
Major Isomer ◽  
Low Concentrations ◽  
Complex Forms ◽  
Dimeric Aggregates

The 1 H NMR spectra of the five-coordinated rhodium phthalocyanine complex Me ( RPc ) Rh (III) (1, RPc = dianion of 1,4,8,11,15,18,22,25-octa-n-pentylphthalocyanine) in toluene indicate that it exists as a discrete monomer at low concentrations. The complex forms a dimer aggregate reversibly in the concentration range of 2.6–10.2 mM at -90 < T < 22 ° C . The dimerization constants at -60, -80, and -90 °C are 2.0 × 102, 5.7 × 102, and 1.0 × 103 M -1, respectively. In chloroform, aggregation of the complex occurs at ~0.3 mM, reflecting the lower solvating power of chloroform for this complex. The 1 H NMR spectra of the chloroform solutions indicate that at concentrations greater than 1.0 mM, two discrete dimers in the ratio of 87:13 are reversibly formed. The 1 H NMR spectra of the major isomer, 2a, suggest that it is the 45 °-staggered cofacial dimer, a dimer with a D4 d symmetry. The 1 H NMR spectra of the minor isomer, 2b, suggest that it is a slipped cofacial dimer with a C2 h symmetry, which is formed by slipping a ( RPc ) Rh plane of the eclipsed dimer (a D4 h dimer) along a line connecting two opposing meso nitrogens of ( RPc ) Rh . Interestingly, the solution conformation of 2b is similar to that of the basic stacking unit found in the crystal structure of 1.

Kristallstruktur und spektroskopische Untersuchung von Mg(GeMe3)2 · 2 DME / Crystal Structure and Spectroscopic Study of Mg(GeMe3)2 · 2 DME

1984 ◽  
Vol 39 (7) ◽  
pp. 855-860 ◽  
Author(s):  
Lutz Rösch ◽  
Carl Krüger ◽  
A .-P. Chiang
Keyword(s):  
Crystal Structure ◽  
Spectroscopic Study ◽  
Nmr Spectra ◽  
X Ray ◽  
H Nmr ◽  
Magnesium Compound ◽  
C Nmr

Mg(GeMe3)2 · 2 DME is synthesized by reaction of Hg(GeMe3)2 with magnesium in 1 ,2 -- dimethoxyethane. The X-ray structure, IR, Raman, 1H NMR , and 13C NMR spectra of this first organogermyl magnesium compound are reported.

Restricted rotation about arene–oxygen bonds in some 1,3-di-tert-butyl-2-methoxyarenedicarbonylphosphorus(III)chromium compounds

1984 ◽  
Vol 62 (11) ◽  
pp. 2566-2569 ◽  
Author(s):  
Eva M. Campi ◽  
Bryan M. K. Gatehouse ◽  
W. Roy Jackson ◽  
Ian D. Rae ◽  
Margaret G. Wong
Keyword(s):  
Crystal Structure ◽  
Low Temperatures ◽  
Nmr Spectra ◽  
Hindered Rotation ◽  
Methyl Group ◽  
Tert Butyl ◽  
H Nmr ◽  
Free Energy Of Activation ◽  
Chromium Compounds ◽  
Related Compounds

The 1H nmr spectra of 1,3-di-tert-butyl-2-methoxybenzenedicarbonyltriphenylphosphinechromium (5) and some related compounds at low temperatures show the presence of two species which interconvert with free energy of activation near 50 kJ mol−1. The species differ in the orientation of the methoxy with respect to the chromium, since the same type of process is observed in a chelate complex in which a phosphinite ligand on chromium is also attached to the arene. Hindered rotation about the arene–chromium axis is not involved. The crystal structure of 5 shows the Ph3P anti to the methoxy and the O-methyl group proximal to chromium.

Synthesis and Crystal Structure of a New Ni2+ Complex1

2012 ◽  
Vol 441 ◽  
pp. 387-391 ◽  
Author(s):  
Yin Zhi Jiang ◽  
Yang Zou ◽  
Lian Qun Zhang
Keyword(s):  
Crystal Structure ◽  
Nmr Spectra ◽  
Crystal Data ◽  
X Ray Diffraction ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
H Nmr ◽  
Coordination Sites ◽  
Assisted Decomposition ◽  
Coordination Reaction

(S,S)-N,N’- bi-(benzal)-1,2-cyclohexanediamine Schiff base (1) was synthesized and characterized by 1 H NMR spectra, MS spectra and IR spectra. And the coordination reaction of 1 with chlorate of Ni(II) was studied. The reaction of 1 with NiII salt [NiCl2] generates a new compound (2). 2 was characterized using IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. Crystal data for 2: space group Coca, with a = 24.580(4)Å, b = 9.5829(13)Å, c = 7.6836(11)Å, α=90.00º, β=90.00º, γ=90.00º, Z=4, V= 1809.8(5)Å3, Dc=1.446 mg.m-3, µ=1.376 mm-1, F(000)=840. There are 6 coordination sites around Ni2+ of 2, which are respectively occupied by two oxygen atoms (all from two H2O molecules) and four nitrogen atoms [all from two 1,2-cyclohexanediamine molecule]. The Ni atom and four chelating nitrogen atoms are coplanar. There exist intra-molecular H-bond and intermolecular H-bond. The mechanism of metal-assisted decomposition of 1 was also discussed briefly.

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