| Autor: |
Chu CK; Arnold and Mabel Beckman Laboratories of Chemical Synthesis , California Institute of Technology , Pasadena , California 91125 , United States., Lin TP; Arnold and Mabel Beckman Laboratories of Chemical Synthesis , California Institute of Technology , Pasadena , California 91125 , United States., Shao H; Department of Chemistry , University of Pittsburgh , Pittsburgh , Pennsylvania 15260 , United States., Liberman-Martin AL; Arnold and Mabel Beckman Laboratories of Chemical Synthesis , California Institute of Technology , Pasadena , California 91125 , United States., Liu P; Department of Chemistry , University of Pittsburgh , Pittsburgh , Pennsylvania 15260 , United States., Grubbs RH; Arnold and Mabel Beckman Laboratories of Chemical Synthesis , California Institute of Technology , Pasadena , California 91125 , United States. |
| Abstrakt: |
Second-generation ruthenium olefin metathesis catalysts bearing aminophosphine ligands were investigated with systematic variation of the ligand structure. The rates of phosphine dissociation ( k 1 ; initiation rate) and relative phosphine reassociation ( k -1 ) were determined for two series of catalysts bearing cyclohexyl(morpholino)phosphine and cyclohexyl(piperidino)phosphine ligands. In both cases, incorporating P-N bonds into the architecture of the dissociating phosphine accelerates catalyst initiation relative to the parent [Ru]-PCy 3 complex; however, this effect is muted for the tris(amino)phosphine-ligated complexes, which exhibit higher ligand binding constants in comparison to those with phosphines containing one or two cyclohexyl substituents. These results, along with X-ray crystallographic data and DFT calculations, were used to understand the influence of ligand structure on catalyst activity. Especially noteworthy is the application of phosphines containing incongruent substituents (PR 1 R' 2 ); detailed analyses of factors affecting ligand dissociation, including steric effects, inductive effects, and ligand conformation, are presented. Computational studies of the reaction coordinate for ligand dissociation reveal that ligand conformational changes contribute to the rapid dissociation for the fastest-initiating catalyst of these series, which bears a cyclohexyl-bis(morpholino)phosphine ligand. Furthermore, the effect of amine incorporation was examined in the context of ring-opening metathesis polymerization, and reaction rates were found to correlate well with catalyst initiation rates. The combined experimental and computational studies presented in this report reveal important considerations for designing efficient ruthenium olefin metathesis catalysts. |
