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Host−guest complexes of cyclopentadienyl iron dicarbonyl (CpFe(CO)2) CO-releasi...

Monteiro, Rodrigo P.; Calhau, Isabel B.; Gomes, Ana C.; Mendes, Ricardo F.; Paz, Filipe A. Almeida; D. Lopes, André; Da Silva, José Paulo

Iron(II) cyclopentadienyl carbonyl complexes are promising as CO-releasing molecules (CORMs) for therapeutic applications. In common with other metallodrugs, the practical application of Fe-CORMs may require their conjugation with biocompatible carriers to improve their bioavailability and protect them from premature degradation. Here, we show that the CO-releasing properties of the complexes [CpFe(CO)2Cl] (1) ...


Inclusion complexes of cucurbit[n]urils (n = 7, 8) with η5 -cyclopentadienyl me...

Neves, Patrícia; Gomes, Ana C.; Monteiro, Rodrigo P.; Santos, Mirela J.; Valente, Anabela A.; D. Lopes, André; Gonçalves, Isabel S.; Pillinger, Martyn

There are very few known examples of supramolecular compounds comprising molybdenum species hosted inside the portals/cavities of cucurbit[n]urils (CBn). In this work, CB7 and CB8 macrocycles have been studied as hosts for the carbonyl complex [CpMo(CO)(3)Me] (1) (Cp = eta(5)-C5H5). Compounds were isolated in the solid state and characterized as genuine 1:1 inclusion complexes (1@CBn) by elemental and thermogra...


Host-guest complexes of cucurbit[8]uril and [(η5-C5H4R)Mo(CO)3CH3] (R = H, CO2C...

Gomes, Ana C.; Monteiro, Rodrigo P.; Calhau, Isabel B.; D. Lopes, André; Gonçalves, Isabel S.; Pillinger, Martyn

The monosubstituted cyclopentadienyl half-sandwich molybdenum(II) tricarbonyl complex [(eta 5-C5H4CO2CH3) Mo(CO)3CH3] (1) and its 1:1 inclusion compound with cucurbit[8]uril (1@CB8) have been prepared and characterised by elemental and thermogravimetric analyses, powder X-ray diffraction, diffuse reflectance UV-vis, solid-state 13C{1H} MAS NMR, FT-IR, and Raman spectroscopies. The CO-releasing behaviours of 1, ...


β-Cyclodextrin and cucurbit[7]uril as protective encapsulation agents of the CO...

Monteiro, Rodrigo P.; Calhau, Isabel B.; Gomes, Ana C.; D. Lopes, André; Da Silva, José Paulo; Gonçalves, Isabel P.; Pillinger, Martyn

The CO releasing ability of the complex [CpMo(CO)3Me] (1) (Cp = eta 5-C5H5) has been assessed using a deoxymyoglobin-carbonmonoxymyoglobin assay. In the dark, CO release was shown to be promoted by the reducing agent sodium dithionite in a concentration-dependent manner. At lower dithionite concentrations, where dithionite-induced CO release was minimised, irradiation at 365 nm with a low-power UV lamp resulted...


Host-guest complexes of cucurbit[8]uril and [(η5-C5H4R)Mo(CO)3CH3] (R = H, CO2C...

Gomes, Ana C.; Monteiro, Rodrigo P.; Calhau, Isabel B.; Lopes, André D.; Gonçalves, Isabel S.; Pillinger, Martyn

The monosubstituted cyclopentadienyl half-sandwich molybdenum(II) tricarbonyl complex [(η5 -C5H4CO2CH3) Mo(CO)3CH3] (1) and its 1:1 inclusion compound with cucurbit[8]uril (1@CB8) have been prepared and characterised by elemental and thermogravimetric analyses, powder X-ray diffraction, diffuse reflectance UV–vis, solid-state 13C{1 H} MAS NMR, FT-IR, and Raman spectroscopies. The CO-releasing behaviours of 1, 1...


An organic-organometallic CO-releasing material comprising 4,4'-bipyridine and ...

Calhau, Isabel B.; Gomes, Ana C.; Mendes, Ricardo F.; Almeida Paz, Filipe A.; Gonçalves, Isabel S.; Pillinger, Martyn

Over the past two decades, following the discovery of the important biological roles of carbon monoxide (CO), metal carbonyl complexes have been intensively studied as CO-releasing molecules (CORMs) for therapeutic applications. To improve the properties of "bare" low molecular weight CORMs, attention has been drawn to conjugating CORMs with macromolecular and inorganic scaffolds to produce CO-releasing materia...


Inclusion complexes of cucurbit[n]urils (n = 7, 8) with η5‐cyclopentadienyl met...

Neves, Patrícia; Gomes, Ana C.; Monteiro, Rodrigo P.; Santos, Mirela J.; Valente, Anabela A.; Lopes, André D.; Gonçalves, Isabel S.; Pillinger, Martyn

There are very few known examples of supramolecular compounds comprising molybdenum species hosted inside the portals/cavities of cucurbit[n]urils (CBn). In this work, CB7 and CB8 macrocycles have been studied as hosts for the carbonyl complex [CpMo(CO)3Me] (1) (Cp = η5-C5H5). Compounds were isolated in the solid state and characterized as genuine 1:1 inclusion complexes (1@CBn) by elemental and thermogravimetr...


Effect of 4,4′-dialkyl-2,2′-bipyridine ligands on the hydrolysis of dichlorodio...

Gomes, Diana M.; Gomes, Ana C.; Neves, Patrícia; Almeida Paz, Filipe A.; Valente, Anabela A.; Gonçalves, Isabel S.; Pillinger, Martyn

Molybdenum catalysts have been industrially recognized for decades for liquid phase epoxidation, which is an important chemical reaction process, since epoxides are used for many industrial applications. In this work, molybdenum oxide hybrid catalysts, prepared by a reflux hydrolysis methodology, performed effectively as heterogeneous catalysts or reaction-induced self-separating catalysts under mild reaction c...


Biobased routes for the upgrading of α-angelica lactone to value added products

Antunes, Margarida M.; Silva, Andreia F.; Skrodczky, Kai; Fernandes, Auguste; Ribeiro, Filipa; Russo, Patricia A.; Pinna, Nicola; Pillinger, Martyn

Biomass derived compounds are important building blocks to produce value added bioproducts. These bioproducts can replace fossil fuel derivatives in a more sustainable approach, contributing to reduce CO2 emissions and a circular economy. More attention has been given to angelica lactone compounds due to their potential to be reduced to gamma-valerolactone (GVL) and other biobased products with several importan...


A Molybdenum(VI) Complex of 5-(2-pyridyl-1-oxide)tetrazole: synthesis, structur...

Nunes, Martinique S.; Gomes, Diana M.; Gomes, Ana C.; Neves, Patrícia; Mendes, Ricardo F.; Paz, Filipe A. Almeida; Lopes, Andre D.; Pillinger, Martyn

The discovery of heterogeneous catalysts synthesized in easy, sustainable ways for the valorization of olefins derived from renewable biomass is attractive from environmental, sustainability, and economic viewpoints. Here, an organic–inorganic hybrid catalyst formulated as [MoO3 (Hpto)]·H2O (2), where Hpto = 5-(2-pyridyl-1-oxide)tetrazole, was prepared by a hydrolysis– condensation reaction of the complex [MoO2...


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