Molybdenum(II) Complexes with -Diimines: Catalytic Activity in Organic and Ionic Liquid Solvents

resumo

The new [MoX((3)-C3H5)(CO)(2)(-diimine)] complexes with: (i) X = Br or triflate and -diimine = 1,10-phenanthroline (phen) and dipyridophenazine (dppz); and (ii) X = Br and -diimine = phen and dppz, with several substituents, are synthesized and characterized. The structures of [MoBr((3)-C3H5)(CO)(2)(Cl-phen)] and [Mo(CF3SO3)((3)-C3H5)(CO)(2)(dppz)] are determined by using single-crystal X-ray diffraction. These and three complexes of 2,2-bipyridyl (bpy), and its two derivatives with Me and tBu substituents, are tested in the homogeneous catalytic epoxidation of several olefins in dichloromethane, exhibiting, in general, a good selectivity towards the respective epoxide and relatively low TOFs. For the first time, the oxidation of cis-cyclooctene with some of these catalysts is also conducted in a variety of room-temperature ionic liquids (RTILs). In the presence of [MoBr((3)-C3H5)(CO)(2)(phen)], the conversions, in general, increase, compared with the reactions in organic solvents. Interestingly, different chemoselectivity is found when [C(6)mim][Ntf(2)] and [C(2)mim][FAP] are used with diol (24-26%). On the other hand, [MoBr((3)-C3H5)(CO)(2)(L)] (L = Me-phen or dppz) exhibits much lower conversions in the RTILs tested than in common organic solvents.

palavras-chave

INHOMOGENEOUS ELECTRON-GAS; OXIDATION CATALYSTS; OLEFIN EPOXIDATION; CARBONYL-COMPLEXES; CORRELATION-ENERGY; HYDROGEN-PEROXIDE; CRYSTAL-STRUCTURE; DYNAMIC-BEHAVIOR; PRECURSORS; DERIVATIVES

categoria

Chemistry

autores

Saraiva, MS; Nunes, CD; Felix, V; Ribeiro, APC; de Castro, CN; Calhorda, MJ

nossos autores

agradecimentos

We thank Fundacao para a Ciencia e a Tecnologia for financial support (UID/MULTI/00612/2013 and UID/QUI/00100/2013). M. S. S. thanks FCT for fellowship SFRH/BPD/88082/2012 and APCR for fellowship SFRH/BPD/90883/2012. The crystallographic studies were supported by CICECO - Aveiro Institute of Materials (UID/CTM/50011/2013), financed by National Funds through the FCT/Ministerio da Ciencia, Tecnologia e Ensino Superior (MCTES) and cofinanced by QREN-FEDER through COMPETE under the PT2020 Partnership.

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