ic8b02917_si_002.pdf (165.35 kB)
Download fileInfluence of Anionic Ligand Exchange in Latent Sulfur-Chelated Ruthenium Precatalysts
journal contribution
posted on 2018-12-04, 00:00 authored by Elisa Ivry, Noy B. Nechmad, Mark Baranov, Israel Goldberg, N. Gabriel LemcoffFour new cis-dianionic S-chelated
ruthenium benzylidenes were synthesized by chloride ligand exchange.
The special cis-dianionic conformation of these complexes contributed
to a particularly facile anion exchange process, producing room-temperature-latent
precatalysts. Their catalytic activity was strongly influenced by
the solvent used. The latent iodide complex very efficiently promoted
ring-closing metathesis by heating in toluene. Conversely, carboxylate
ligands produced quite poor catalysts, but could abstract chlorides
from chlorinated solvents to transform into active precatalysts. In
tetrahydrofuran (THF), the S-chelated dichloro complex was shown to
promote cycloisomerization instead of metathesis; however, the metathesis
activity in THF could be recovered in the presence of phenylacetylene
as a cocatalyst. Under the same conditions, all the other complexes
required addition of LiCl to mimic this dichotomous behavior.
History
Usage metrics
Read the peer-reviewed publication
Categories
Keywords
ring-closing metathesismetathesis activityLatent Sulfur-Chelated Ruthenium PrecatalystsTHFanion exchange processS-chelated dichlorochloride ligand exchangeroom-temperature-latent precatalystscomplexcarboxylate ligandscis-dianionic conformationcis-dianionic S-chelated ruthenium benzylideneschlorinated solventsAnionic Ligand Exchangedichotomous behavior