Mixed diphosphine/diamine ruthenium (II) isomers: synthesis, structural characterization and catalytic hydrogenation of ketones
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2018
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The complexes trans-[RuCl2(dppb)(cydn)] (1), trans-[RuCl2(dppb)(opda)] (2) and cis-[RuCl2(dppb)(cydn)] (3) were synthesized from [{RuCl2(dppb)}2-μ-(dppb)] {where: dppb = 1,4-bis(diphenylphosphino)butane; cydn = cis and trans (±) 1,2-diaminocyclohexane, and opda = o-phenylenediamine}. The complexes were characterized by nuclear magnetic resonance of phosphorus (31P{1H} NMR), cyclic voltammetry (CV), infrared and ultraviolet/visible spectra (IR and UV/vis) as well as elemental analyses (CHN). The X-ray structures of (1) and (3) were determined and they are presented here. DFT calculations and experimental data showed that the trans isomers are obtained as thermodynamic products while the cis isomers are kinetic products. This behavior is different than described in the literature for similar complexes, where the cis isomer is obtained from the trans isomer. Additionally, the catalytic activity of the complexes (1), (2) and (3) was investigated, as pre-catalysts, in the reduction of the acetophenone and 4-methylacetophenone by transfer-hydrogenation.
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NASCIMENTO, Rebecca D. et al. Mixed diphosphine/diamine ruthenium (II) isomers: synthesis, structural characterization and catalytic hydrogenation of ketones. Journal of Molecular Structure, Amsterdam, v. 1151, p. 277-285, 2017. DOI: 10.1016/j.molstruc.2017.09.044. Disponível em: https://www.sciencedirect.com/science/article/abs/pii/S0022286017312231?via%3Dihub. Acesso em: 29 jan. 2024.