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. 2009 Jun 17;131(23):7962-3.
doi: 10.1021/ja902738u.

Z-selective olefin metathesis processes catalyzed by a molybdenum hexaisopropylterphenoxide monopyrrolide complex

Margaret M Flook  1 , Annie J Jiang, Richard R Schrock, Peter Müller, Amir H Hoveyda
Affiliations

Z-selective olefin metathesis processes catalyzed by a molybdenum hexaisopropylterphenoxide monopyrrolide complex

Margaret M Flook et al. J Am Chem Soc. .

Abstract

The molybdenum-based monoaryloxide monopyrrolide (MAP) species, Mo(NAd)(CHCMe(2)Ph)(C(4)H(4)N)(HIPTO) (2a), which contains "small" imido (Ad = 1-adamantyl) and "large" aryloxide (HIPTO = O-2,6(2,4,6-i-Pr(3)C(6)H(2))C(6)H(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.

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Figures

Figure 1
Figure 1
Thermal ellipsoid drawing of W(NAr)(C3H6)(C4H4N)(HIPTO) (50% probability). Hydrogen atoms are removed for clarity except for those on C1, C2, C3, and two of the twelve HIPTO isopropyl methyl carbons.
See this image and copyright information in PMC

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