Z-Selective Olefin Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylterphenoxide Monopyrrolide Complex
Author(s)Flook, Margaret M.; Jiang, Annie J.; Hoveyda, Amir H.; Schrock, Richard Royce; Muller, Peter
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The molybdenum-based monoaryloxide monopyrrolide (MAP) species, Mo(NAd)(CHCMe[subscript 2]Ph)(C[subscript 4]H[subscript 4]N)(HIPTO) (2a), which contains “small” imido (Ad = 1-adamantyl) and “large” aryloxide (HIPTO = O-2,6(2,4,6-i-Pr[subscript 3]C[subscript 6]H[subscript 2])C[subscript 6]H[subscript 3]) ligands, catalyzes Z-selective metathesis reactions as a consequence of intermediate metallacyclobutane species not being able to have an (anti) substituent pointing toward the HIPTO group. Ring-opening metathesis polymerization (ROMP) of dicarbomethoxynorbornadiene (DCMNBD) with 2% 2a in toluene leads to >99% cis and >99% syndiotactic poly(DCMNBD), while ROMP of cyclooctene and 1,5-cyclooctadiene (300 equiv) with initiator 2a leads to poly(cyclooctene) and poly(cyclooctadiene) that have cis contents of >99%; all are previously unknown microstructures. Z-Selectivity is also observed in the metathesis of cis-4-octene and cis-3-hexene by initiator 2a to give cis-3-heptene.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
Journal of the American Chemical Society
American Chemical Society (ACS)
Flook, Margaret M., Annie J. Jiang, Richard R. Schrock, Peter Muller, and Amir H. Hoveyda. “Z-Selective Olefin Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylterphenoxide Monopyrrolide Complex.” Journal of the American Chemical Society 131, no. 23 (June 17, 2009): 7962-7963.
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