Transfer hydrogenation of N-benzylideneaniline catalyzed by ruthenium complexes with pincer-type phosphorus nitrogen ligands using propan-2-ol as the hydrogen source

Abstract

, et al.. Transfer hydrogenation of N-benzylideneaniline catalyzed by ruthenium complexes with pincer-type phosphorus nitrogen ligands using propan-2-ol as the hydrogen source. Catalysis Communications, Elsevier, 2017, 99, pp.150-153. <10.1016/j.catcom.2017.04.026>. <hal-01578552>A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT A C C E P T E D M A N U S C R I P T AbstractRuthenium complexes containing phosphorus-nitrogen, pincer-type (NPN) ligands show high activities and selectivities in the transfer hydrogenation of Nbenzylideneaniline using propan-2-ol as the hydrogen source. Such is the case of complexes RuCl 2 PPh 3 (PPh(NHPy) 2 ) (1) and RuCl 2 PPh 3 (PPh(NHPyMe) 2 ) (2) which also show TOFs 5989 h -1 and 5928 h -1 , respectively. These remarkable results were obtained after only 10 minutes of reaction using a 1000/1 substrate/catalyst ratio. ACCEPTED MANUSCRIPT A C C E P T E D M A N U S C R I P T IntroductionTransfer hydrogenation of ketones has several advantages over using molecular hydrogen in homogeneous catalysis. The former makes use of simple equipment, low catalyst loading, safe manipulation, and easy removal of volatile by-products. The good performance of [RuCl 2 (diphosphane)(diamine)] complexes in the asymmetric hydrogenation of ketones [1] has increased the great interest to study the reaction looking at the reactivity of Ru (II) complexes based on phosphorus and amino ligands [2,3].

Ruthenium(II)–carbonyl complexes containing two N-monodentate 1,8-naphthyridine ligands: active catalysis in transfer hydrogenation reactions

“…Our group has previously studied the mechanism for transfer hydrogenation using ruthenium(II) compounds containing pincer phosphorusnitrogen ligands, where the ruthenium hydride (Ru-H) intermediate was detected by proton nuclear magnetic resonance ( 1 H NMR) during the catalytic reaction. The broad signal detected at À14.46 ppm (Moya et al, 2017) was attributed to very reactive ruthenium hydride species, which reacts in the presence of any substrate or even solvent. The crystal structures of both complexes display cis-Cl and monodentate 1,8-naphthyridine.…”

Selective hydrogenation of furfural to furfuryl alcohol catalysed by ruthenium complexes containing phosphorus‐nitrogen ligands

“…The N-P-N ligands and their corresponding ruthenium (II) complexes (Ru-1 and Ru-2, Figure 1) were synthesized following protocols reported by our group of investigators. [23,24] Catalytic essays were monitored by a GC analysis using a Perkin Elmer Clarus 580 GC chromatograph with a flame ionisation detector (FID) and equipped with an Elite-5 column. The product of the catalytic reaction was characterized using mass spectroscopy (GC-MS).…”

“…Our research group has successfully explored the hydrogenation of imines and other substrates using ruthenium and palladium complexes containing phosphorous-nitrogen ligands. [23,24] These ligands combine the coordinating properties of phosphorous and nitrogen (both with different affinities towards the central metal ion), thus providing highly stable catalysts in the processes of carbonylation and hydrogenation.…”

Ruthenium(II) half-sandwich complexes containing N-substituted 5-nitrobenzimidazole: Synthesis, structures and catalytic transfer hydrogenation of ketones

“…Bu reaksiyonda çözücü olarak 2propanol (i-propil alkol) kullanılmaktadır. Ketonların hidrojen transferinde 2-propanolün en çok tercih edilmesinde; güvenirliliği, toksik olmaması, yüksek seçiciliği, ucuzluğu, ulaşılabilirliği, reaksiyon sonucu oluşan ürünün kolay uzaklaşması ve çevre dostu olması gibi üstün özellikleri etkili olmuştur [15][16][17][18]. Ayrıca ketonların katalitik transfer hidrojenasyonu, ilaç, zirai ilaç, aroma, koku, malzeme ve hassas kimya endüstrileri için değerli sonuç ürünleri ve öncüleri olan kiral bileşikler de dahil olmak üzere çok çeşitli alkollerin üretimi için temel ve kilit işlemdir [19,20].…”

“…Keton olarak p-kloroasetofenon kullanıldığında 2c, 2d, 2f komplekslerinde bağlı grupların sayısı katalizörlerin aktifliklerini oldukça etkilemiş, fakat bağlı grupların elektronik etkisi katalizörlerin aktifliklerini pek fazla etkilememiştir (Çizelge 1. deney no:17,18,20). Keton olarak p-bromoasetofenon kullanıldığında, 2c kompleksinin düşük katalitik aktivite gösterdikleri tespit edilmiştir (Çizelge 1. deney no: 15).…”