56237-13-9Relevant academic research and scientific papers
METALS IN ORGANIC SYNTHESIS. XIV. NMR, IR, AND REACTIVITY STUDIES ON THE OLEFIN HYDROFORMYLATION CATALYZED BY Pt-Sn COMPLEXES
Scrivanti, Alberto,Berton, Adriano,Toniolo, Luigi,Botteghi, Carlo
, p. 369 - 384 (1986)
Among the several hydrides formed when trans- (L=PPh3) reacts with SnCl2, only trans- rapidly inserts ethylene, at -80 deg C, to yield cis-.At -10 deg C, cis- irreversibly rearranges to the trans-isomer, thus indicating that the cis-isomer is the kinetically controlled species, and that the trans-isomer is thermodynamically more stable.At -50 deg C, a mixture of trans- and trans- reacts with ethylene to give cis- and this has been attributed to the catalytic activity of SnCl2 which dissociates from cis- at this temperature.Carbon monoxide promotes the cis-trans isomerization of cis-, which occurs rapidly even at -80 deg C.This rearrangement is followed by a slower reaction leading to the cationic complex trans-(1+)SnCl3(1-).At -80 deg C, this complex does not react further, but when it is kept at room temperature ethyl migration to coordinated carbon monoxide takes place, to give several Pt-acyl complexes, i.e. trans-, trans-, trans-, and trans-(1+)SnCl3(1-).This mixture of Pt-acyl complexes reacts with molecular hydrogen to yield n-propanal and the same complex mixture of platinum hydrides as is obtained by treating trans- with SnCl2.
METALS IN ORGANIC SYNTHESES. X. OLEFIN HYDROFORMYLATION AND HYDROCARBOALKOXYLATION COMPETITIVELY CATALYZED BY A /SnCl2 SYSTEM
Cavinato, G.,Toniolo, L.
, p. 275 - 280 (2007/10/02)
The system /SnCl2 significantly catalyzes only the hydroformylation of α-olefins at 100 deg C in EtOH, at P(CO)=P(H2)=65 atm; hydrocarboalkoxylation does not occur to an apreciable extent, even in the presence of potential activating agents (HCl, LiCl).The catalyst precursor has been recovered from the reaction medium, as the cationic complex (SnCl3), having the SnCl3- anion non-directly bound to the platinum atom, and as trans-.The latter complex is a (precursor) intermediate leading to an active catalytic species possessing at least one Pt-Sn bond which plays a key role in the catalysis.
