New Molybdenum(II) Complexes with alpha-Diimine Ligands: Synthesis, Structure, and Catalytic Activity in Olefin Epoxidation


Three new complexes [Mo(eta(3)-C3H5)Br(CO)(2){(PrN)-Pr-i=C(R)C5H4N}], where R = H (IMP = N-isopropyl 2-iminomethylpyridine), Me, and Ph, were synthesized and characterized, and were fluxional in solution. The most interesting feature was the presence, in the crystal structure of the IMP derivative, of the two main isomers (allyl and carbonyls exo), namely the equatorial isomer with the Br trans to the allyl and the equatorial with the Br trans to one carbonyl, the position trans to the allyl being occupied by the imine nitrogen atom. For the R = Me complex, the less common axial isomer was observed in the crystal. These complexes were immobilized in MCM-41 (MCM), following functionalization of the diimine ligands with Si(OEt)(3), in order to study the catalytic activity in olefin epoxidation of similar complexes as homogeneous and heterogeneous catalysts. FTIR, C-13- and Si-29-NMR, elemental analysis, and adsorption isotherms showed that the complexes were covalently bound to the MCM walls. The epoxidation activity was very good in both catalysts for the cis-cyclooctene and cis-hex-3-en-1-ol, but modest for the other substrates tested, and no relevant differences were found between the complexes and the Mo-containing materials as catalysts.




Biochemistry & Molecular Biology; Chemistry


Vasconcellos-Dias, M; Marreiros, J; Sales, R; Felix, V; Brandao, P; Nunes, CD; Calhorda, MJ

nossos autores


This research was funded by Fundacao para a Ciencia e a Tecnologia, Portugal, (UID/MULTI/00612/2013). The crystallographic studies were supported by CICECO-Aveiro Institute of Materials (UID/CTM/50011/2019), financed by National Funds through the FCT/MEC, and co-financed by QREN-FEDER through COMPETE under the PT2020 Partnership Agreement.

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