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.

Polycarboxylate crown ethers from meso-tartaric acid

1991 ◽  
Vol 69 (1) ◽  
pp. 12-19 ◽  
Author(s):  
Frank R. Fronczek ◽  
Richard D. Gandour ◽  
Thomas M. Fyles ◽  
Philippa J. Hocking ◽  
Susan J. McDermid ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Crown Ether ◽  
Tartaric Acid ◽  
Crown Ethers ◽  
Nmr Spectra ◽  
Product Distribution ◽  
Complexing Agents ◽  
Triclinic Space Group ◽  
The Stability ◽  
Ether Synthesis

The synthesis of crown ethers derived from meso-tartaric acid was investigated. The sodium salt of the bis(dimethylamide) of meso-tartaric acid reacted with diethylene glycol ditosylate to give a mixture of 18-crown-6 tetraamide and 27-crown-9 hexaamide crown ethers. The 2R,3S,11S,12R 18-crown-6 isomer crystallized in triclinic space group [Formula: see text] (a = 7.557(2), b = 8.866(2), c = 10.4133(13) Å, α = 94.13(2), β = 95.86(2), γ = 99.26(2)°, R = 0.040 for 2090 observed of 3129 unique reflections). The structures of the remaining products were then assigned from the NMR spectra. The solution conformations of the amide crown ethers were examined by NMR, and provide a rationale for the product distribution obtained. One of the 18-crown-6 isomers and a mixture of the two 27-crown-9 isomers were hydrolyzed to the respective crown ether carboxylic acids, and the stability constants for complexation of cations were determined by potentiometric titration. The meso tetra- and hexacarboxylates are remarkably nonselective and inefficient cation complexing agents, compared to related crown ethers from R,R-(+)-tartaric acid, due to the unfavorable conformational control exerted by the tartaro units. Key words: crown ether synthesis, complexation, crown ether conformation, meso-tartaric acid, crystal structure.

scholarly journals Linkage of α-cyclodextrin-terminated poly(dimethylsiloxanes) by inclusion of quasi bifunctional ferrocene

2013 ◽  
Vol 9 ◽  
pp. 1278-1284 ◽  
Author(s):  
Helmut Ritter ◽  
Berit Knudsen ◽  
Valerij Durnev
Keyword(s):  
Electron Microscopy ◽  
Mass Spectrometry ◽  
Light Scattering ◽  
Ir Spectroscopy ◽  
Nmr Spectra ◽  
H Nmr ◽  
Scattering Measurements ◽  
End Groups ◽  
2D Roesy ◽  
2D Roesy Nmr

We report the noncovalent linkage of terminally substituted oligo(dimethylsiloxanes) bearing α-cyclodextrins (α-CD) as host end groups for the cyclopentadienyl rings of ferrocene. This double complexation of unsubstituted ferrocene leads to a supramolecuar formation of the siloxane strands. Structural characterization was performed by the use of 1H NMR and IR spectroscopy and by mass spectrometry. Electron microscopy studies and dynamic light scattering measurements show a significant decrease of the derivative size after the complexation with ferrocene. In addition, further evidence for the successful complexation of the end groups was verified by the shifts of the protons in the 1H NMR spectra and in the correlation signals of the 2D ROESY NMR spectra.

Synthese und Kristallstruktur von [VCl2(15-Krone-5)]+[VOCl4]- / Synthesis and Crystal Structure of [VCl2(15-Crown-5)]+[VOCl4]-

1990 ◽  
Vol 45 (10) ◽  
pp. 1393-1397 ◽  
Author(s):  
Gerlinde Frenzen ◽  
Werner Massa ◽  
Thilo Ernst ◽  
Kurt Dehnicke
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Crown Ether ◽  
Single Crystals ◽  
Structure Determination ◽  
Acetonitrile Solution ◽  
Tetragonal Symmetry ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
Ether Molecule

[VCl2(15-crown-5)]+[VOCl4]- has been prepared by the reaction of VCl4 with 15-crown-5 in acetonitrile solution in the presence of water, forming black-brown single crystals. They were characterized by IR spectroscopy as well as by an X-ray structure determination. Space group Pnma, Z = 4, 1530 observed unique reflexions, R = 0.052. Lattice dimensions at -120°C: a = 1128.5(4), b = 1063.3(3), c = 1680(1) pm. The compound forms ions, in which the cation contains vanadium(+III), which is seven coordinate by the five oxygen atoms of the crown ether molecule and by two chlorine atoms in axial positions of a pentagonal bipyramide. The [VOCl4]- anion contains vanadium (+V) with approximately tetragonal symmetry

Die Kristallstruktur von [Na4(OSiPh3)4(H2O)3] / The Crystal Structure of [Na4(OSiPh3)4(H2O)3]

1996 ◽  
Vol 51 (11) ◽  
pp. 1583-1586 ◽  
Author(s):  
A. Mommertza ◽  
K. Dehnickea ◽  
J. Magull
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Single Crystals ◽  
Coordination Number ◽  
Structure Determination ◽  
Title Compound ◽  
Saturated Solution ◽  
Crystal Structure Determination ◽  
Humid Atmosphere ◽  
Space Group

Colourless single crystals of the title compound are obtained from a saturated solution of NaOSiPh3 in toluene in a humid atmosphere. We have characterized [Na4(OSiPh3)H2O)3] by IR spectroscopy and by a crystal structure determination. Space group R3, Z = 6 , R = 0.056. Lattice dimensions at -70°C: a = b = 1540.3 pm, c = 2639.6 pm. The compound has the structure of a Na4O4 heterocubane which is only slighty distorted and in which one of the sodium atoms is not hydrated and shows coordination number three.

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.

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.

Ein gemischtvalentes Oxometallat mit Cr3+ anstelle von Ti3+: Ba2Ti44+Cr2O13 / A Mixed Valent Oxometallate with Cr3+ Instead of Ti3+ Ba2Ti44+ Cr2O13

1994 ◽  
Vol 49 (7) ◽  
pp. 911-914 ◽  
Author(s):  
S. Möhr ◽  
Keyword(s):  
Crystal Structure ◽  
High Temperature ◽  
Single Crystals ◽  
Lattice Energy ◽  
Structure Type ◽  
Oxidation States ◽  
X Ray ◽  
High Temperature Reactions ◽  
The Stability

Abstract Single crystals of Ba2Ti3+Cr2Oi3 were prepared by C02-LASER high temperature reactions and investigated by X-ray work. The compound crystallizes with monocli­nic symmetry, a = 15.0185, b = 3.9419, c = 9.0764 Å. β = 98.137°, Z = 2. Ba2Ti4Cr2O13 is isotypic to Na2Ti6O13. The crystal structure is discussed with respect to ordered or disordered distributions of Ti4+ and Cr3+ using calculations of Coulomb terms of lattice energy. It is shown, that the stability of this structure type will be decre­ased by replacement of Na+ by ions with higher oxidation states.

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.

Electronic structure of low-spin six-coordinate iron(III) meso-tetrapropylchlorin complexes

2014 ◽  
Vol 18 (08n09) ◽  
pp. 778-791 ◽  
Author(s):  
Akira Ikezaki ◽  
Jyunpei Ono ◽  
Yoshiki Ohgo ◽  
Mari Fukagawa ◽  
Takahisa Ikeue ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Ground State ◽  
Nmr Spectra ◽  
Spectroscopic Properties ◽  
H Nmr ◽  
Axial Ligands ◽  
Splitting Parameter ◽  
Nmr Signals ◽  
Electronic Ground ◽  
C Nmr

Low-spin iron(III) tetrapropylchlorins [ Fe ( T n PrC ) L 2]± (L = HIm, 1-MeIm, DMAP, CN-, 4-CNPy, tBuNC) adopt the dxy-type ground state regardless of the nature of axial ligands. Among the complexes examined, [ Fe ( T n PrC )( t BuNC )2]+ has shown quite unique spectroscopic properties as described below. (1) 1 H NMR signals were extremely broad as compared with those of other complexes. In particular, 5,20- CH 2(α) signal was too broad to detect. (2) No signals except C γ were observed in 13 C NMR spectra. (3) Tetragonal splitting parameter (|Δ|) estimated by the EPR g values at 4.2 K reached as much as 12.4 λ, which is the largest |Δ| value among all the low-spin iron(III) porphyrins and porphyrinoids reported previously. On the basis of these results, we have concluded that [ Fe ( T n PrC )( t BuNC )2]+ adopts the low-spin iron(III) with (dxz, dyz)4(dxy)1 electronic ground state at 4.2–30 K where the EPR spectra are taken, while it should be expressed as the low-spin Fe ( II ) chlorin π-radical cation [ Fe II ( T n PrC .)( t BuNC )2]+ at ambient temperature where the NMR spectra are taken.

Sign in / Sign up

Export Citation Format

Share Document