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)
Fa. Jalon et al., 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), Journal of organometallic chemistry, 508(1-2), 1996, pp. 69-74
The reaction of [RuHCl(bpzm)(cod)] (1) (bpzm = bis(pyrazol-1-yl)methan
e, 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)(c
od)]CF3SO3 (3a), which isomerizes easily to cis-[RuH(PMe(2)Ph)(bpzm)(c
od)]CF3SO3 (3b), while a similar reaction of 1, in the presence of AgC
F3SO3, gave a series of phosphine-containing complexes such as [RuH(CF
3SO3)(cod)(PMe(2)Ph)(2)] (4), the products of this process greatly dep
ending on the reaction conditions. The complex trans-[RuH{P(OMe)(3)}(b
pzm)(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 AgCF3SO
3) with N-donors pyridine, 4-methylpyridine (4-picoline) or 3,5-dimeth
ylpyridine (3,5-lutidine) yielded a mixture of products which we belie
ve to contain both cis- and trans-[RuHL(bpzm)(cod)]CF3SO3 (L = pyridin
e, 4-picoline, or 3-5-lutidine). Spectroscopic data are provided for t
hese compounds. Complex 1 catalyzes both the hydrogenation of the unsa
turated substrates cyclohexene, cyclohexanone, acetone and propanal, w
ith turn-over rates of up to 1506 h(-1) for cyclohexanone in the prese
nce 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).