title: Moving from Classical Ru-NHC to Neutral or Charged Rh-NHC Based Catalysts in Olefin Metathesis.
abstract: Considering the versatility of oxidation states of rhodium together with the successful background of ruthenium-N-heterocyclic carbene based catalysts in olefin metathesis, it is envisaged the exchange of the ruthenium of the latter catalysts by rhodium, bearing an open-shell neutral rhodium center, or a +1 charged one. In the framework of in silico experiments, density functional theory (DFT) calculations have been used to plot the first catalytic cycle that as a first step includes the release of the phosphine. DFT is, in this case, the tool that allows the discovery of the less endergonic reaction profile from the precatalytic species for the neutral catalyst with respect to the corresponding ruthenium one; increasing the endergonic character when dealing with the charged system.
authors: Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona, Catalonia, Spain. albert.poater@udg.edu.
authors: Albert
authors: A
authors: Poater
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D006571:Heterocyclic Compounds / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry
chemical_list: D000475:Alkenes; D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; C030011:carbene; D012428:Ruthenium; D012238:Rhodium; D008697:Methane
keywords: DFT; N-heterocyclic carbene; initiation; interchange; olefin metathesis; rhodium; ruthenium