Molybdenum and tungsten alkylidene complexes for cis- and trans-selective ring-opening metathesis polymerization
Massachusetts Institute of Technology. Department of Chemistry.
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Chapter 1 describes the synthesis of tert-butylimido alkylidene complexes for molybdenum and tungsten. A dimer species [chemical formula] served as a bisimido precursor. After alkylation with Grignard reagent, alkylidene formation is accomplished using pyridinium chloride. [chemical formula] crystallizes as a dimer [chemical formula] with a loss of pyridine for each W center. For the case of molybdenum, addition of pentafluorophenol to the diimido dialkyl precursor affords [chemical formula]. Dipyrrolide complexes for both Mo and W are synthesized and isolated as a 2,2'-bipyridine adduct. Addition of a sterically encumbered terphenol along with ZnCl₂(dioxane) affords monoalkoxide pyrrolide (MAP) complexes [chemical formula]. Chapter 2 investigates Z-selective ring-opening metathesis polymerization (ROMP) of 3- substituted cyclooctenes (3-RCOEs) by Mo and W MAP catalysts. [chemical formula], [chemical formula], and [chemical formula] all produced >98% [chemical formula]. The key in forming high molecular weight polymer instead of cyclic oligomer species was to run the reaction neat. Surprisingly, the fastest initiator was [chemical formula] among all three MAP species. Polymerization proceeds via a propagating species in which the R group is of C2 position of the propagating chain, giving HT polymers with high regioselectivity. Chapter 3 describes the synthesis and reactivity of compounds containing a tert-butylimido ligand. Chelating alkylidenes can be synthesized either by alkylidene exchange or by traditional routes in forming alkylidene complexes from diimido dialkyl species. A W MAP complex containing a chelating alkylidene can be synthesized and its reactivity is comparable to that of neopentylidene analogue in 1-octene homocoupling. Complexes with a chelating diolate ligand [chemical formula] and [chemical formula] were synthesized. However, attempts to remove the pyridine ligand induced C-H activation of one tertbutyl group on Biphen ligand to form alkyl complexes. Chapter 4 presents the synthesis of high sequence-regular alternating trans-AB copolymers by ROMP initiated by [chemical formula]. Monomers employed were 2,3-dicarbomethoxy-7-isopropylidenenorbomadiene (B), [chemical formula] (B'), cyclooctene (A), and cycloheptene (A'). All four combinations afford structures containing a high degree of monomer alternation. Evidence suggests a catalytic cycle proceeding through a syn alkylidene arising from insertion of B (syn-MB) reacting with A to form an anti alkylidene (anti-MA) and a trans-AB linkage. A MAP complex [chemical formula] [chemical formula] was also found to form trans-poly[A-alt-B'] with >90% alternating dyad sequences. Variations on imido and alkoxide ligands were surveyed as well as both A and B type monomers.
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2015.Cataloged from PDF version of thesis.Includes bibliographical references.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
Massachusetts Institute of Technology