Estudo sobre o mecanismo de reações de hidrogenação em complexos do tipo [RuCl2(P)2(N)2][(P)2= mono ou bifosfina; N= piridina ou derivados]

Abstract

In this study, it was performed synthesis and characterization of the complexes of general formula cis-[RuCl2(PPh3)2(N)2], cis-[RuCl2(PPh3)2(N-N)], trans- [RuCl2(dppb)(N)2], cis-[RuCl2(dppb)(N-N)] and cis-[RuCl2(P-P)(N-N)] [PPh3 = triphenylphosphine, dppb = 1,4-bis(diphenylphosphino)butane, (P-P) = bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane and 1,3- bis(diphenylphosphino)propane, N = pyridine (py), 4-picoline (4-pic), 4-tertbutilpyridine (4t-Bupy ), 4-vinylpyridine (4-vpy) and 4-phenylpyridine (4-Phpy), N-N = 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,4'-dimethyl-2,2'-bipyridine (4- Mebipy), di-2-piridilcetona (dpk) and 4,4'-dimethoxy-2,2'-bipyridine (MeO-bipy)]. The characterizations were performed using elemental analysis, conductivity, Infrared spectrometry (IR), NMR 31P {1H}, cyclic voltammetry and differential pulse voltammetry as well as X-ray diffraction, when suitable crystals were obtained. Kinetic studies of substitution of one chloride ligand from the coordination sphere of the complex by a monodentate L ligand (pyridine (py) or 4-picoline (4-pic)) were performed for the complex series of cis-[RuCl2(P-P)(N-N)] in terms of pseudo-first order conditions. The catalytic studies of some of the complex obtained in this work in hydrogenation reactions of cyclohexene were carried out. For the catalytic reactions were used a stainless steel reactor purging with H2 pressure, temperature and agitation were controlled and the analysis of results were performed in a gas chromatograph with detector flame ionization detector (GC-FID) with a capillary column DB5. The catalytic reactions performed with the complex series of [RuCl2(PPh3)2(N)2] showed a high conversion of reactant (cyclohexene - CXE) to product (cyclohexane - CXA) and a high value of TOF (turnover frequency) above 1000 h-1, during 24 hours of reaction. For complex series of [RuCl2(dppb)(N)2] the values of conversion (%) and TOF (h-1) were not as high, but still significant. For the other tested complexes, the values were low and the conversions were not significant.