Z-Selective Olefin Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylterphenoxide Monopyrrolide Complex
| Autor: | Margaret M. Flook, Annie J. Jiang, Amir H. Hoveyda, Peter Müller, Richard R. Schrock |
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| Rok vydání: | 2009 |
| Předmět: |
Molybdenum
General Chemistry ROMP Alkenes Metathesis Biochemistry Medicinal chemistry Article Catalysis chemistry.chemical_compound Colloid and Surface Chemistry chemistry Cyclooctene Organometallic Compounds Salt metathesis reaction Organic chemistry Ring-opening metathesis polymerisation Cyclooctadiene Group 2 organometallic chemistry Acyclic diene metathesis |
| Zdroj: | Journal of the American Chemical Society. 131:7962-7963 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | 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 to99% cis and99% 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 of99%; 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. |
| Databáze: | OpenAIRE |
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