title: Olefin metathesis in supercritical carbon dioxide.
abstract: Liquid or supercritical carbon dioxide (scCO(2)) is a versatile reaction medium for ring-opening metathesis polymerization (ROMP) and ring-closing olefin metathesis (RCM) reactions using well-defined metal catalysts. The molybdenum alkylidene complex 1 and ruthenium carbenes 2 and 3 bearing PCy(3) or N-heterocyclic carbene ligands, respectively, can be used and are found to exhibit efficiency similar to that in chlorinated organic solvents. While compound 1 is readily soluble in scCO(2), complexes 2 and 3 behave like heterogeneous catalysts in this reaction medium. Importantly, however, the unique properties of scCO(2) provide significant advantages beyond simple solvent replacement. This pertains to highly convenient workup procedures both for polymeric and low molecular weight products, to catalyst immobilization, to reaction tuning by density control (RCM versus acyclic diene metathesis polymerization), and to applications of scCO(2) as a protective medium for basic amine functions. The latter phenomenon is explained by the reversible formation of the corresponding carbamic acid as evidenced by (1)H NMR data obtained in compressed CO(2). Together with its environmentally and toxicologically benign character, these unique physicochemical features sum up to a very attractive solvent profile of carbon dioxide for sustainable synthesis and production.
authors.affiliation: Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim/Ruhr, Germany.
authors.forename: A
authors.initials: A
authors.lastname: Fürstner
authors.forename: L
authors.initials: L
authors.lastname: Ackermann
authors.forename: K
authors.initials: K
authors.lastname: Beck
authors.forename: H
authors.initials: H
authors.lastname: Hori
authors.forename: D
authors.initials: D
authors.lastname: Koch
authors.forename: K
authors.initials: K
authors.lastname: Langemann
authors.forename: M
authors.initials: M
authors.lastname: Liebl
authors.forename: C
authors.initials: C
authors.lastname: Six
authors.forename: W
authors.initials: W
authors.lastname: Leitner