SYNTHESIS AND SPECTROSCOPIC STUDIES OF NEW HYDRIDORUTHENIUM COMPLEXES - CATALYTIC REACTIONS OF [RUHCL(BPZM)(COD)] (BPZM=BIS(PYRAZOL-1-YL)METHANE, COD=CYCLOOCTA-1,5-DIENE)

摘要

The reaction of [RuHCl(bpzm)(cod)] (1) (bpzm = bis(pyrazol-1-yl)methane, cod = cycloocta-1,5-diene) with one equivalent of AgCF3SO3 afforded the triflate-containing [RuH(CF3SO3)(bpzm)(cod)] (2). The reaction of 2 with PMe(2)Ph allowed the synthesis of trans-[RuH(PMe(2)Ph)(bpzm)(cod)]CF3SO3 (3a), which isomerizes easily to cis-[RuH(PMe(2)Ph)(bpzm)(cod)]CF3SO3 (3b), while a similar reaction of 1, in the presence of AgCF3SO3, gave a series of phosphine-containing complexes such as [RuH(CF3SO3)(cod)(PMe(2)Ph)(2)] (4), the products of this process greatly depending on the reaction conditions. The complex trans-[RuH{P(OMe)(3)}(bpzm)(cod)]CF3SO3 (5a), which also readily isomerizes to cis-[RuH{P(OMe)(3)}(bpzm)(cod)]CF3SO3 (5b), was isolated from the reaction of 2 with P(OMe)(3), or alternatively from the reaction of 1 with P(OMe)(3) and AgCF3SO3, Finally, the reaction of 2 or 1 (in the presence of AgCF3SO3) with N-donors pyridine, 4-methylpyridine (4-picoline) or 3,5-dimethylpyridine (3,5-lutidine) yielded a mixture of products which we believe to contain both cis- and trans-[RuHL(bpzm)(cod)]CF3SO3 (L = pyridine, 4-picoline, or 3-5-lutidine). Spectroscopic data are provided for these compounds. Complex 1 catalyzes both the hydrogenation of the unsaturated substrates cyclohexene, cyclohexanone, acetone and propanal, with turn-over rates of up to 1506 h(-1) for cyclohexanone in the presence of NaOH at 130 degrees C, and the efficient transfer hydrogenation of cyclohexanone by propan-2-ol in the presence of NaOH at 80 degrees C, with a turn-over rate of 880 h(-1). [References: 28]