| Summary: | Chapter 1. Ring-Opening Alkyne Metathesis Polymerization of Dibenzocyclooctynes
A molybdenum(VI) propylidyne substituted with bidentate phenoxides will react with dibenzocyclooctynes in living ring-opening alkyne metathesis polymerization (ROAMP). The corresponding monodentate phenoxides do not yield well-controlled polymerizations. However, if the substrate in the ROAMP reaction is an aliphatic cyclooctyne, uncontrolled, non-living polymerizations take place in all cases.
Chapter 2. Ring-Opening Alkyne Metathesis via a Tungstenatetrahedrane Intermediate
A cyclopropenone-modified dibenzocyclooctyne will undergo a single ring opening alkyne metathesis reaction in the presence of Schrock's tris(tert-butoxy)tungsten(VI) neopentylidyne--a highly active alkyne metathesis catalyst. Despite the enormous amount of ring strain present in and related diphenycyclooctadiynes, these compounds do not readily undergo ring-opening alkyne metathesis polymerization (ROAMP), even with the most active alkyne metathesis catalysts available. The ring-opening of 1 proceeds via a tungstenatetrahedrane intermediate. Because of its sluggish reactivity, we were able to follow the ring-opening reaction by NMR to gain mechanistic insight into this remarkable behavior.
Chapter 3. Functionaliztion of Diphenyloligoenes
Bromine and carboxylic acid substituted α,ω-diphenyl-µ,ν-dicyano-oligoenes (DPDCn) were synthesized up to 9 and 7 olefin units in length, respectively. The carboxylic acid functionalized oligoenes (DPDCn-CO2H) are aligned through hydrogen bonding to DMF in the solid state. These can also be used to direct monolayer formation of Fe3O4 on single crystalline, 100 Gallium Arsenide.
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