Z-selective ring-opening metathesis polymerization of 3-substituted cyclooctenes by monoaryloxide pyrrolide imido alkylidene (MAP) catalysts of molybdenum and Tungsten

Ring-opening metathesis polymerization of a series of 3-substituted cyclooctenes (3-MeCOE, 3-HexCOE, and 3-PhCOE) initiated by various Mo and W MAP complexes leads to cis,HT-poly(3-RCOE) polymers. The apparent rate of polymerization of 3-HexCOE by W(N-t-Bu)(CH-t-Bu)(Pyr)(OHMT) (1c; Pyr = pyrrolide; OHMT = O-2,6-Mesityl₂C₆H₃) is greater than the rate of polymerization by Mo(N-t-Bu)(CH-t-Bu)(Pyr)(OHMT) (1b), but both gave the same cis,HT polymer structures. Formation of HT-poly(3-RCOE) employing 1c takes place via propagating species in which the R group (methyl, hexyl, or phenyl) is on C2 of the propagating alkylidene chain, a type of intermediate that has been modeled through the preparation of W(N-t-Bu)(CHCHMeEt)(Pyr)(OHMT). The rate of ROMP is exceedingly sensitive to steric factors: e.g., W(N-t-Bu)(CH-t-Bu)(Me₂Pyr)(OHMT), the dimethylpyrrolide analogue of 1c, essentially did not polymerize 3-HexCOE at 22 C. When a sample of W(N-t-Bu)(CHCHMeEt)(Pyr)(OHMT) and 3-methyl-1-pentene in CDCl₃ is cooled to -20 C, the alkylidene resonances for W(N-t-Bu)(CHCHMeEt)(Pyr)(OHMT) disappear and resonances that can be ascribed to protons in a syn_α/syn_α′ disubstituted trigonal bipyramidal metallacyclobutane complex appear. 3-Methyl-1-pentene is readily lost from this metallacycle on the NMR time scale at room temperature.