New insights about the host–guest chemistry of the tungsten oxo complex of calix[4]arene, and novel "one pot" difunctionalizations of calix[4]arene using tetrachlorometal(VI) oxide (M = Mo, W)

2004 ◽  
Vol 82 (10) ◽  
pp. 1452-1461 ◽  
Author(s):  
Pascal Mongrain ◽  
Jasmin Douville ◽  
Jonathan Gagnon ◽  
Marc Drouin ◽  
Andreas Decken ◽  
...  
Keyword(s):  
Water Molecule ◽  
Lewis Acid ◽  
Chemical Shifts ◽  
Strong Interactions ◽  
Ir Absorption ◽  
One Pot ◽  
X Ray ◽  
Strong Lewis Acid ◽  
Successful Removal ◽  
Coordinated Water

The strong Lewis acid tungsten oxo complex of calix[4]arene can be obtained in both hydrated and non-hydrated forms. This complex coordinates a water molecule inside the cavity via strong O···W interactions with relatively short distances of 2.284(4) and 2.329(2) Å for the tungsten oxo complex of calix[4]arene··H2O·aniline (1), and the tungsten oxo complex of calix[4]arene·H2O·toluene (2·toluene), respectively. The strong interactions are also deduced by the relatively high H2O elimination temperature observed by TGA and DSC (above 200 °C). The coordinated water molecule inside the calix[4]arene cavity is characterized by a strong IR absorption at 3616 cm–1, and a narrow resonance at ~1.2 ppm (the chemical shifts of the uncoordinated water are 1.55 and 1.60 ppm in C6D6 and CDCl3, respectively). This water molecule gives rise to H-bonds with aniline in 1. The tungsten oxo complex of 5,11,17,23-tetrabromocalix[4]arene (4), also binds H2O as the characteristic signatures are observed. The successful removal of H2O in 2, is performed under mild conditions using bis(tetrahydrofuran)-uranyl nitrate as a competitive Lewis acid. When this reaction is performed in acetonitrile, butyronitrile or tert-butylnitrile, the corresponding tungsten oxo complexes of calix[4]arene·acetonitrile (3), ·butyronitrile (5), and ·tert-butylnitrile (6) are obtained. The use of uranyl as a H2O abstractor is unprecedented. The X-ray structure of 3 consists of a tungsten oxo complex of calix[4]arene coordinated by an acetonitrile molecule (d(W···N = 2.412(2) Å). The tetra-5,11,17,23-choromethyl-25,26,27,28-tetrahydroxycalix[4]arene reacts with M(O)Cl4 (M = Mo, W) in a 1:1 stoichiometry, via a tetra Friedel–Crafts addition of benzene or toluene, followed by a lower-rim complexation of the metal oxide, to form "flower-shaped" calix[4]arenes. This "one pot" double functionalization is unprecedented.Key words: calix[4]arene, tungsten, molybdenum, X-ray, host–guest, Friedel–Crafts, Lewis acid, uranyl, DSC, TGA.

A one-dimensional coordination polymer based on Cd2O2clusters: poly[aqua(μ3-4,4′-sulfonyldibenzoato)(3,4,7,8-tetramethyl-1,10-phenanthroline-κ2N,N′)cadmium(II)]

2013 ◽  
Vol 69 (3) ◽  
pp. 244-246 ◽  
Author(s):  
Jian-Qing Tao
Keyword(s):  
Water Molecule ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
Chain Polymer ◽  
One Dimensional ◽  
X Ray ◽  
Acid Ligand ◽  
Carboxylate Groups ◽  
Metal Organic ◽  
Coordinated Water

In the title mixed-ligand metal–organic polymeric complex [Cd(C14H8O6S)(C16H16N2)(H2O)]n, the asymmetric unit contains a crystallographically unique CdIIatom, one doubly deprotonated 4,4′-sulfonyldibenzoic acid ligand (H2SDBA), one 3,4,7,8-tetramethyl-1,10-phenanthroline (TMPHEN) molecule and one water molecule. Each CdIIcentre is coordinated by two N atoms from the chelating TMPHEN ligand, three O atoms from monodentate carboxylate groups of three different SDBA2−ligands and one O atom from a coordinated water molecule, giving a distorted CdN2O4octahedral geometry. Single-crystal X-ray diffraction analysis reveals that the compound is a one-dimensional double-chain polymer containing 28-membered rings based on Cd2O2clusters, with a Cd...Cd separation of 3.6889 (4) Å. These chains are linked by O—H...O and C—H...O hydrogen bonds to form a three-dimensional supramolecular framework. The framework is reinforced by π–π and C—O...π interactions.

scholarly journals Crystal structure of a zwitterionic azaallyl zirconiumamide complex bearing a Zr+-μ-CH3—B− moiety and one equivalent of n-hexane as a solvent

IUCrData ◽  
2018 ◽  
Vol 3 (5) ◽  
Author(s):  
Nils Frerichs ◽  
Christian Adler ◽  
Marc Schmidtmann ◽  
Rüdiger Beckhaus
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Lewis Acid ◽  
Tetrahedral Coordination ◽  
X Ray Diffraction ◽  
Coordination Environment ◽  
X Ray ◽  
Strong Lewis Acid ◽  
Distorted Tetrahedral Coordination

The zirconiumamide complex [(cyclohex-1-enyl)cyclohexylamido]bis(dicyclohexylamido)[methyltris(pentafluorophenyl)borato]zirconium(IV) hexane monosolvate, [Zr{N(C6H11)2}2{N(C6H11)(C6H9)}{BCH3(C6F5)3}]·C6H14, is zwitterionic and bears a Zr+—μ-CH3—B− moiety. The reaction of tris(dicyclohexylamido)methylzirconium with the strong Lewis acid tris(pentafluorophenyl)borane results in the formation of an azaallyl zirconium motif by the loss of H2 in one dicyclohexylamido ligand, as shown by single-crystal X-ray diffraction. The ZrIV cation is coordinated to the N atoms of two dicyclohexylamido ligands, the π-system of one azaallyl ligand, and to the μ-CH3—B unit, resulting in a distorted tetrahedral coordination environment. The Zr—N distance to the azaallyl ligand is elongated, whereas the Zr—C distance to this moiety is found to be shortened in comparison with those to the two Cy2N groups (Cy is C6H11).

Selective chemistry of tripentaerythritol — Synthesis of acetals and their derivatives

2006 ◽  
Vol 84 (4) ◽  
pp. 516-521 ◽  
Author(s):  
Hussein Al-Mughaid ◽  
T Bruce Grindley
Keyword(s):  
Lewis Acid ◽  
Chemical Shifts ◽  
X Ray ◽  
Nmr Chemical Shifts ◽  
X Ray Crystallography ◽  
Catalysed Reaction ◽  
Toluenesulfonic Acid ◽  
C Nmr

Tripentaerythritol was converted efficiently into 2′,2′′:6′,6′′:10′,10′′-tri-O-cyclohexylidene-2,2,6,6,10,10-hexakis(hydroxymethyl)-4,8-dioxa-1,11-undecandiol (4) by the toluenesulfonic acid catalysed reaction with cyclohexanone in a mixture of N,N-dimethylformamide and benzene. Reaction of tripentaerythritol with benzaldehyde under similar conditions gave an easily separated mixture of the four possible stereoisomers. Structures of these stereoisomers were assigned based on 1H and 13C NMR chemical shifts using trends previously observed for the dibenzylidene acetals of dipentaerythritol, whose structures had been established unambiguously by X-ray crystallography. It was found that reduction of the mixture of benzylidene acetals to 2,6,10-tris(benzyloxymethyl)-4,8-dioxa-1,11-undecanediol could be accomplished using triethylsilane with ethylaluminium dichloride as the Lewis acid after a number of commonly used conditions for this transformation failed.Key words: pentaerythritol, tripentaerythritol, dipentaerythritol, acetals, benzylidene acetals, reduction.

scholarly journals Design, Construction, and Characterization of a New Regioisomer and Diastereomer Material Based on the Spirooxindole Scaffold Incorporating a Sulphone Function

Symmetry ◽  
2020 ◽  
Vol 12 (8) ◽  
pp. 1337 ◽  
Author(s):  
Abdullah Mohammed Al-Majid ◽  
Saied M. Soliman ◽  
Matti Haukka ◽  
M. Ali ◽  
Mohammad Shahidul Islam ◽  
...  
Keyword(s):  
Chemical Shifts ◽  
Cycloaddition Reaction ◽  
X Ray Diffraction ◽  
One Pot ◽  
Catalyst Synthesis ◽  
X Ray ◽  
Reactivity Descriptors ◽  
Three Component Reaction ◽  
Hirshfeld Analysis ◽  
Donor Acceptor

The 1,3-dipolar cycloaddition reaction is one of the most rapid, and efficient protocols to access, and construct highly divergent heterocycle chiral auxiliaries. Free catalyst synthesis of spirooxindole scaffold incorporating sulphone moiety via one pot–three component reaction of 6-chloro-isatin, L-proline, and the phenylvinylsulphone as dienophile is presented. The new regioisomer and diastereomer was isolated by precipitation without the tedious purification step, and then characterized via NMR and single crystal X-ray diffraction analysis. Using Hirshfeld analysis, the analysis of molecular packing was performed. It depended mainly on strong O…H and N…H interactions, and weak H…H, C…H, and Cl…H interactions as well. DFT calculations were used to optimize the experimental X-ray structure, which was found well matched with the calculated one. Reactivity descriptors based on the energies of the highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbitals were calculated. Additionally, the donor–acceptor interactions which stabilized the system via σ–σ*, π→π*, n→σ* and n→π* electron delocalization processes were also computed using NBO calculations. The net interaction energies are 49.96, 235.38, 179.66 and 107.06 kJ/mol, respectively. Additionally, the calculated NMR chemical shifts correlated well with the experimental data (R2=0.99).

Composés d'addition de SbF5 avec H2O et HF. Formation d'ions hydronium

1974 ◽  
Vol 52 (11) ◽  
pp. 2077-2084 ◽  
Author(s):  
B. Bonnet ◽  
J. Roziere ◽  
R. Fourcade ◽  
G. Mascherpa
Keyword(s):  
Thermal Analysis ◽  
Differential Thermal Analysis ◽  
Water Molecule ◽  
The Other ◽  
Thermal Treatments ◽  
Analysis Study ◽  
X Ray ◽  
Donor Acceptor ◽  
Thermal Analysis Study ◽  
Coordinated Water

A differential thermal analysis study of solutions of SbF5 in H2O and HF has enabled us to determine the thermal treatments required to obtain the stable crystalline phases: SbF5•2H2O, 4SbF5•5H2O, SbF5•H2O, 3SbF5•2H2O, and SbF5•HF•2H2O.The SbF5 adducts were characterized by X-ray powder diagrams.The vibrational spectra of SbF5•2H2O and SbF5•HF•2H2O are consistent with the ionic structures H3O+SbF5OH− and H5O2+SbF6−.The other hydrates are simple donor-acceptor complexes with the structure H2O → SbF5, in which one water molecule is coordinated to the SbF5 and the others are bound by hydrogen bonds to the coordinated water molecule.

Gesteuerte Kristallisation des Gadolinium(III)-Komplexes von Diethylentriaminpentaacetat: Monomere und dimere Struktur / Controlled Crystallization of the Gadolinium(III) Complex of Diethylenetriamine-Pentaacetate: Monomeric and Dimeric Structure

1998 ◽  
Vol 53 (9) ◽  
pp. 955-959 ◽  
Author(s):  
Robert Ruloff ◽  
Thomas Gelbrich ◽  
Eberhard Hoyer ◽  
Joachim Sieler ◽  
Lothar Beyer
Keyword(s):  
Water Molecule ◽  
Crystal Structures ◽  
Coordination Number ◽  
X Ray ◽  
Dimeric Structure ◽  
Carboxylate Oxygen ◽  
Metal Atoms ◽  
Controlled Crystallization ◽  
Coordinated Water ◽  
Oxygen Atoms

We present the preparation and X-ray crystal structures of two gadolinium(III) complexes of the ligand diethylenetriamine pentaacetic acid (H5dtpa). With two equivalents of guanidinium (gu+) per equivalent of complex we obtained the dimer (gu)4[Gd2(dtpa)2]·(gu)HCO3 , and with one equivalent of aminoguanidinium (agu+) the monomer (agu)[Gd(Hdtpa)(H2O)]·2H2O , both with the metal atoms in a coordination number of 9. The dimer contains no coordinated water molecule. The monomer is present as two crystallographically independent complexes hydrogen-bridged via carboxylate oxygen atoms (O···O 2.48 Å; O-H···O 172°) and with Gd-Ocoord. water distances of 2.418(4) and 2.423(4) Å, respectively.

Complexes of 1,2,4-Triazoles, Part XVII The Crystal Structure of Tris-μ-(4-ethyl-1,2,4-triazole-N1,N2)- (4-ethyl-1,2,4-triazole-N1)-aquo-bis [bis(thiocyanato-N)- nickel(II)]hydrate, Ni2(C4N3H7)4(H2O)(NCS)4 ·H2O(x ≃ 2.5)

1981 ◽  
Vol 36 (7) ◽  
pp. 809-813 ◽  
Author(s):  
Ger Vos ◽  
Anthonie J. de Kok ◽  
Gerrit C. Verschoor
Keyword(s):  
Crystal Structure ◽  
Water Molecule ◽  
The Other ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
Coordinated Water

Abstract The crystal structure of Ni2(C4N3H7)4(H2O)(NCS)4 · 2.5 H2O has been determined by X-ray diffraction techniques. The compound crystallizes in the monoclinic space group P21/n with a = 15.121(4), b= 13.237(2), c= 18.069(3), β = 94.71(2)° and Z = 4; R = 0.040 (Rm = 0.051). The compound consists of dimeric units in which two Ni ions are bridged by three ethyltriazole (Ettrz) groups. For one Ni, two N donating NCS- groups and an Ettrz coordinating by only one N atom complete the NiNe octahedron. The other Ni atom, which is also octahedrally coordinated, has a coordinated water molecule instead of a monodentate Ettrz.

scholarly journals Synthesis, Structure, and Catalytic Activity of A New Mn(II) Complex with 1,4-Phenylenediacetic Acid and 1,10-Phenanthroline

2018 ◽  
Vol 13 (1) ◽  
pp. 1 ◽  
Author(s):  
Li Hua Wang ◽  
Peng Fei Li
Keyword(s):  
Catalytic Activity ◽  
Maximum Yield ◽  
Chain Structure ◽  
Water Molecules ◽  
Single Crystal Diffraction ◽  
One Pot ◽  
Complex Molecules ◽  
X Ray ◽  
1D Chain ◽  
Coordinated Water

A new Mn(II) complex material has been synthesized by one-pot reaction of Mn(CH3COO)2·4H2O, 1,4-phenylenediacetic (H2L), 1,10-phenanthroline (phen), and NaOH in water/ethanol (v:v = 1:1) solution. The structure of Mn(II) complex was determined by elemental analysis, FTIR, and X-ray single-crystal diffraction analysis. The results reveal that Mn(II) complex was constructed by a monodentate 1,4-phenylenediacetate ligand, two phen ligands, a coordinated water molecule, 0.5 uncoordinated 1,4-phenylenediacetate ligand and six uncoordinated water molecules. The complex molecules form 1D chain structure by the π-π interaction of phen molecules. The catalytic activity of Mn(II) complex for coupling of benzaldehyde, phenylacetylene and piperidine in 1,4-dioxane has also been  investigated  and the maximum yield of propargylamine is up to 72.2 % after 12 h at 120 oC. Copyright © 2017 BCREC Group. All rights reservedReceived: 5th March 2017; Revised: 7th June 2017; Accepted: 12nd July 207; Available online: 22nd January 2018; Published regularly: 2nd April 2018How to Cite: Wang, L.H., Li, P.F. (2018). Synthesis, Structure, and Catalytic Activity of A New Mn(II) Complex with 1,4-Phenylenediacetic Acid and 1,10-Phenanthroline. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1): 1-6 (doi:10.9767/bcrec.13.1.975.1-6) 

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