Reversible Inhibition/Activation of Olefin Metathesis:  A Kinetic Investigation of ROMP and RCM Reactions with Grubbs' Catalyst

The metathesis activity of Grubbs' catalyst 1 was investigated in the presence of N-donor ligands (1-methylimidazole [MIM], 4-(N,N-dimethylamino)pyridine [DMAP], pyridine, and 1-octylimidazole [OIM]). Ring opening metathesis polymerization (ROMP) reactions of cyclooctene (COE), bulk-ROMP reactions of COE and norbornadiene (NBD), and ring closing metathesis (RCM) reactions of diethyl diallylmalonate (DEDAM) were conducted containing various equivalents of N-donor with respect to catalyst. ROMP reactions could be stopped using MIM (1-5 equiv) and DMAP (2-5 equiv), and slowed with pyridine (1-5 equiv) by factors >100, in benzene solution for 24 h. The stopped reactions could be initiated with excess phosphoric acid (H3PO4), and the reactions proceeded faster than with uninhibited Grubbs' catalyst in the first 4 min after reactivation. Thereafter, the reaction proceeded at the same rate as the reaction with the uninhibited catalyst. ROMP reactions in neat COE and NBD could be inhibited for 72 h using 2 equiv of MIM, DMAP, or OIM and activated with H3PO4 to give polymer gels within minutes or less. RCM reactions could be completely inhibited with MIM (1-5 equiv), but upon treatment with H3PO4, the reaction would proceed at a fraction of the initial rate accomplished by uninhibited Grubbs' catalyst 1. A structural investigation of the inhibited species showed that MIM and DMAP completely or partially transform catalyst 1 into the hexacoordinate species 5a or 5b producing free PCy3, which additionally acts as an inhibitor for the ROMP reaction. Upon reactivation, the PCy3 is protonated along the N-donor ligand; however, over the period of 5 min, the phosphine has been found to coordinate back to the ruthenium catalyst. Therefore, the reaction slows to the same polymerization rate as the reaction using the uninhibited catalyst at this point. Complexes 5a and 5b were isolated, characterized, and employed in ROMP and RCM experiments where they exhibited very low catalytic activity.