Homogeneous hydrogenation with new cationic ruthenium(II) complexes of [RuH(CO)(NCCH3)(PPh3)2(diphos)]+ and [RuH(CO)(NCCH3)(PPh3)(diphos)]+. Crystal structure of [RuH(CO)(NCCH3)(PPh3) (Fe(η5-C5H4PPh2) 2)][BF4]

Article abstract of DOI:10.1016/0277-5387(96)00103-9

A series of ruthenium(II) complexes [RuH(CO)(NCCH₃)(PPh₃)₂(diphos)][BF₄] (diphos: = dppm, Ph₂PCH₂PPh₂ (2); dppe = Ph₂PCH₂CH₂PPh₂ (3); = dppp, Ph₂PCH₂ CH₂CH₂PPh₂ (4); = dppb, Ph₂PCH₂CH₂CH₂CH₂PPh ₂ (5)) and [RuH(CO)(NCCH₃) (PPh₃)(diphos)][BF₄] (diphos: = dppe (6); = dppp (7); = dppb (8); = dppf, Fe(η⁵-C₅H₄PPh₂)₂ (9)) was prepared from the reaction of [RuH(CO)(NCCH₃)₂(PPh₃)₂] [BF₄] and diphos ligands by changing the reaction conditions. These complexes have been characterized by analytical and spectroscopic (IR and ¹H NMR) methods. The structure of [RuH(CO)(NCCH₃)(PPh₃)(dppf)][BF₄] (9) has been determined by X-ray crystallography. The homogeneous hydrogenations of propanal to propan-1-ol catalyzed by complexes 2-9 have been investigated at 90°C and 20 atm hydrogen pressure. The catalytic activities of the chelating diphosphine species 6-9 were dependent upon the structure of the complex as well as upon the ring sizes of the chelates. Copyright