abstract
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 thermogravimetric analyses, powder X-ray diffraction, scanning electron microscopy, C-13{H-1} cross-polarization magic-angle spinning NMR, FT-IR, Raman, and diffuse reflectance UV-Vis spectroscopies. The host-guest structures can act as supramolecular precatalysts for olefin epoxidation. Based on the model reaction of cis-cyclooctene with hydroperoxide oxidants (tert-butylhydroperoxide or hydrogen peroxide), the structural features of 1@CBn as well as the operating conditions influence the catalytic process. The metal species in 1@CBn undergo oxidative decarbonylation in situ, giving oxidized metal species that are catalytically active for olefin epoxidation. The type of oxidant and solvent influences the catalytic activity and stability. 1@CB8 was more stable than 1@CB7 with regard to catalyst recycling and reuse. Based on the substrate scope investigation, for relatively large olefins, such as the fatty acid methyl ester methyl oleate, the size of the macrocyclic host may be a determining factor for catalytic activity.
keywords
OLEFIN EPOXIDATION; BETA-CYCLODEXTRIN; OXIDATION; ALKYL; HYDROGENATION; CYCLOOCTENE; TUNGSTEN
subject category
Chemistry
authors
Neves, P; Gomes, AC; Monteiro, RP; Santos, MJ; Valente, AA; Lopes, AD; Gonçalves, IS; Pillinger, M
our authors
Ana Catarina Costa Gomes Alves
Assistant Researcher
Anabela Tavares Aguiar Valente
Principal Researcher
Isabel Maria de Sousa Gonçalves
Associate Professor
Martyn Pillinger
Principal Researcher
Patrícia dos Santos Neves
Assistant Researcher
Rodrigo Pinto Monteiro
PhD StudentProjects
Collaboratory for Emerging Technologies, CoLab (EMERGING TECHNOLOGIES)
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
CICECO - Aveiro Institute of Materials (UIDP/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
acknowledgements
CICECO - Aveiro Institute of Materials, Grant/Award Numbers: UIDB/50011/2020, UIDP/50011/2020, LA/P/0006/2020; FCT/MCTES, Grant/Award Number: CEECIND/02128/2017; European Social Fund, Grant/Award Number: 2020.04758.BD