Zn-Al layered double hydroxides (LDHs) intercalated by terephthalate (TPH) and biphenyl-4,4'-dicarboxylate (BPH) anions have been synthesized by direct co-precipitation from aqueous solution. The Zn/Al ratio in the final materials was 1.8. The products were characterized by powder X-ray diffraction, thermogravimetric analysis, FTIR and FTRaman spectroscopy, and MAS NMR spectroscopy. The basal spacing for the TPH-LDH intercalate was 14.62 A, indicating that the guest anions stack to form a monolayer with the aromatic rings perpendicular to the host layers. For the LDH intercalate containing BPH anions, a basal spacing of at least 19.2 A would be expected if the anions adopted an arrangement similar to that for the TPH anions. The observed spacing was 18.24 A, suggesting that the anions are tilted slightly with respect to the host layers.

Thermogravimetric analysis

Layered double hydroxides

Source

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Citations (11)

Structural Studies of β‐Cyclodextrin and Permethylated β‐Cyclodextrin Inclusion Compounds of Cyclopentadienyl Metal Carbonyl Complexes

European Journal of Inorganic Chemistry (2006)

Susana S. Braga Filipe A. Almeida Paz Martyn Pillinger João Seixas Carlos C. Romão

Abstract [CpM(CO) n Cl] complexes with M = Fe ( n = 2) and Mo ( n = 3) have been immobilised in plain β‐cyclodextrin (β‐CD) and permethylated β‐CD (TRIMEB) by methods tailored according to the stabilities and solubilities of the individual components. Four adducts were obtained with a 1:1 host/guest stoichiometry. The compounds were studied by powder X‐ray diffraction (XRD), thermogravimetric analysis (TGA), 13 C{ 1 H} CP/MAS NMR and FTIR spectroscopy. A comparison of the experimental powder XRD data for the TRIMEB/[CpMo(CO) 3 Cl] inclusion compound with reference patterns revealed that the crystal packing is very similar to that reported previously for a TRIMEB/ethyl laurate inclusion compound. The unit‐cell parameters refined to a = 14.731, b = 22.476, c = 27.714 Å (volume = 9176.3 Å 3 ), and the space group was confirmed as P 2 1 2 1 2 1 . A hypothetical structural model of the inclusion compound was subsequently obtained by global optimisation using simulated annealing. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Thermogravimetric analysis

Cyclopentadienyl complex

Powder Diffraction

Stoichiometry

Inclusion compound

10.1002/ejic.200501006

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Citations (30)

Synthesis and characterisation of a RuII([14]aneS4) complex immobilised in MCM-41-type mesoporous silica

Journal of the Chemical Society Dalton Transactions (2001)

Martyn Pillinger Isabel S. Gonçalves André D. Lopes João Madureira Paula Ferreira

Ruthenium(II) complexes containing the macrocycle 1,4,8,11-tetrathiacyclotetradecane ([14]aneS4) and nitrogen-coordinated nitrile ligands were prepared using cis-[Ru(DMSO)4Cl2] as the starting material. The first synthetic step consisted of introduction of the thioether ligand to give [Ru([14]aneS4)(DMSO)Cl]Cl. Substitution of the DMSO ligand by the nitrile ligands NCCH3 or NC(CH2)3Si(OEt)3 (L) gave the complexes [Ru([14]aneS4)(L)Cl]X (X = Cl−, PF6−). Introduction of the triethoxysilyl ligand allowed the [Ru([14]aneS4)Cl]+ fragment to be tethered to the surface of the ordered mesoporous silica MCM-41 by pore volume impregnation of a solution of the complex in dichloromethane. A high metal loading was achieved (0.56 mmol g−1). Powder XRD and N2 adsorption studies of the derivatised material indicated that the textural properties of the support were preserved during the grafting experiment and that the channels remained accessible, despite a large reduction in both surface area and pore volume (ca. 50%). IR, UV/VIS, photoluminescence and MAS NMR spectroscopy (13C, 29Si) confirmed that the structural integrity of the RuII complex was retained during immobilisation, except for loss of ethoxide groups due to the reaction with pendant silanols on the silica surface.

Thioether

Dichloromethane

10.1039/b101152i

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Citations (20)

Organotin–Oxometalate Coordination Polymers as Catalysts for the Epoxidation of Olefins

Journal of Catalysis (2002)

Marta Abrantes Anabela A. Valente Martyn Pillinger Isabel S. Gonçalves João Rocha

Cyclooctene

Dichloromethane

10.1006/jcat.2002.3619

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Citations (48)

Dichloro and dimethyl dioxomolybdenum(VI)-bipyridine complexes as catalysts for oxidative desulfurization of dibenzothiophene derivatives under extractive conditions

Journal of Organometallic Chemistry (2022)

Diana Julião Ana C. Gomes Luís Cunha‐Silva Martyn Pillinger Isabel S. Gonçalves

The complexes [MoO2Me2(2,2′-bipyridine)] (5), [MoO2X2(4,4′-dimethyl-2,2′-bipyridine)] (X = Cl (2), Me (6)), [MoO2Me2(4,4′-di‑tert‑butyl‑2,2′-bipyridine)] (7) and [MoO2X2(4,4′-dinonyl-2,2′-bipyridine)] (X = Cl (4), Me (8)) have been prepared and examined as catalysts in extractive and catalytic oxidative desulfurization (ECODS) of a simulated diesel fuel (3000 ppm S) containing dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. The molecular structures of 6 and 8 were characterized by 1H NMR, FT-IR and FT-Raman, and X-ray crystallography. The ECODS reaction conditions were optimized for complex 5 by comparing different extraction solvents (MeCN, the ionic liquid (IL) 1‑butyl‑3-methylimidazolium hexafluorophosphate ([BMIM]PF6), polyethylene glycol (PEG) and two PEG-based deep eutectic solvents), and by varying the catalyst and oxidant (H2O2) amounts, and diesel/solvent volume ratio. Under the optimal conditions with [BMIM]PF6 as the extraction solvent, the quantitative elimination of all sulfur compounds from the model diesel was achieved within 3 h at 70 °C. A comparison of initial ECODS rates for complexes 2, 4, 6 and 8 indicated that the equatorial N,N-chelate ligand was more important than the axial ligand (X) for the desulfurization catalytic performance, with the best results being obtained for the IL-soluble complexes 4 and 8. The IL-entrapped catalyst from 4 showed a good capacity to be reused in consecutive desulfurization cycles.

Dibenzothiophene

Hexafluorophosphate

Bipyridine

10.1016/j.jorganchem.2022.122336

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Citations (4)

Multiply Bonded Dimolybdenum Cation Immobilized in Mesoporous Silica: XAFS Analysis and Catalytic Activity in Cyclopentadiene Polymerization

Macromolecular Rapid Communications (2001)

Martyn Pillinger Isabel S. Gonçalves Paula Ferreira João Rocha Marcus Schäfer

MCM-41 derivatized with the cis-[Mo2(μ-O2CMe)2(MeCN)6]2+ cation has been characterized by means of XAFS spectroscopy and shown to be active as an initiator for the cationic polymerization of methylcyclopentadiene. The Mo-Mo quadruple bond is not disrupted during the fixation on the surface.

Cationic polymerization

Cyclopentadiene

10.1002/1521-3927(20011101)22:16<1302::aid-marc1302>3.0.co;2-5

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Citations (22)

Solid-state study of the structure and host–guest chemistry of cucurbituril-ferrocene inclusion complexes

Dalton Transactions (2016)

Ana C. Gomes Clara I. R. Magalhães Tânia S. M. Oliveira André D. Lopes Isabel S. Gonçalves

Solid-state host–guest interactions have been investigated for cucurbit[n]uril-ferrocene inclusion compounds (n = 7, 8) prepared via a microwave-assisted hydrothermal approach.

Cucurbituril

Host–guest chemistry

10.1039/c6dt02811j

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Citations (16)