cis/trans Coordination in Olefin Metathesis by Static and Molecular Dynamic DFT Calculations

• DOI: 10.1007/s10593-014-1491-6
• Publication Date: 2014-05-24T05:12:31Z
• Authors: A. Poater; A. Correa; E. Pump; L. Cavallo
• Keywords: organometallic chemistry; Metathesis (Chemistry); Funcional de densitat, Teoria del; Catalysts; Olefin metathesis; Organic Chemistry; Catalitzadors; Aliphatic compounds; Química organometàl·lica; Cis/trans isomers; Cis/trans isomers; Grubbs catalyst; N-heterocyclic carbene; Olefin metathesis; Organometallic chemistry; Organic Chemistry; 01 natural sciences; 7. Clean energy; Grubbs catalyst; N-heterocyclic carbene; cis/trans isomers; olefin; metathesis; organometallic chemistry; RUTHENIUM CARBENE COMPLEXES; THEORETICAL PERSPECTIVE; QUINOXALINE; COMPLEXES; GRUBBS-TYPE; CATALYSTS; MECHANISM; LIGANDS; ENERGY; CIS; RELEVANT; 0104 chemical sciences; Grubbs catalyst; Organometallic chemistry; Metàtesi (Química); cis/trans isomers; olefin metathesis; N-heterocyclic carbene; Compostos alifàtics; Density functionals

L. Cavallo thanks the INSTM (CINECA Grant) for financial support. A. Poater thanks the Spanish MINECO for a Ramon y Cajal contract (RYC-2009-05226) and European Commission for a Career Integration Grant (CIG09-GA-2011-293900)<br/>In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity<br/>