Hydroformylation-hydrogenation and hydroformylation-acetalization reactions catalyzed by ruthenium complexes

Abstract

In this work, the catalytic activity of ruthenium II and III complexes containing chloride, pyridine, phosphine and CO ligands was investigated in the hydroformylation – hydrogenation and hydroformylation – acetalization reactions. The complexes mer-[RuCl₃(dppb)(H₂O)](1), mer-[RuCl₃(dppb)(4-Vpy)](2), mer-[RuCl₃(dppb)(4-tBupy)](3), mer-[RuCl₃(dppb)(py)](4), mer-[RuCl₃(dppb)(4-Phpy)](5), mer-[RuCl₃(dppb)(4-Mepy)](6), cis-[RuCl₂(CO)₂(dppb)](7), trans-[RuCl₂(CO)₂(dppb)](8), RuCl₃·xH₂O(9), [RuCl₂(PPh₃)₃](10) and [RuCl₂(PPh₃)₂(dppb)](11) were used as supplied or synthesized as previously described in the literature {Where PPh₃ = triphenylphosphine, dppb = 1,4-bis(diphenylphosphino)butane, py = pyridine, 4-Mepy = 4-methylpyridine, 4-Vpy = 4-vinylpyridine, 4-tBupy = 4-tert-butylpyridine and 4-Phpy = 4-phenylpyridine}. These complexes were used as a pre-catalysts in a hydroformylation catalytic system to produce CC, CO and CO bonds, where 1-decene resulted in a formation of respective alcohol and dimethyl acetals. Several reactions were performed in order to find the best reaction conditions presenting the best conversion (64% after 24 h). The 1-decene was also used as a substrate in two type tandem reactions labeled as: hydroformylation – hydrogenation (HH) and hydroformylation – acetalization (HA) reactions. The relationship between Ru – catalyst/substrate was 1:100, without free ligands or additives, in a controlled temperature and pressure. All the products of catalytic reactions HH and HA were analyzed by CG-FID with good yields.