Structure-function relationships of copper and molybdenum complexes

The crux of this research: structure-function relationships of transition metal complexes. Firstly, working to further predecessor’s findings using borane-substituted N-heterocyclic carbenes (NHCs) to modulate the emission of copper complexes. The second project focused on understanding the mechanistic consequences of ligand changes on a molybdenum isomerization catalyst scaffold. Although the methods were dramatically different, the core was still the same: Can structural changes be made to predictably modify the activity of complexes?The thermodynamics of isomerization reactions dictate that the E-isomer is favored over the Z-isomer. Although the E-isomer can be a useful product, this is a well-researched isomerization to form a thermodynamically favored product. There are fewer catalysts for isomerization to Z-alkenes, found in synthetic targets and further transformations. The Dobereiner Lab developed molybdenum (0) catalysts, published in 2018 and 2023, capable of Z-2 selective isomerization of terminal olefins. Both required acid additives to initiate the isomerization reaction and were not widely tolerant of functionalized substates. While other research groups have reported catalysts capable of Z- selective isomerization- there are consistent issues with 2-alkene and Z-alkene retention over reaction time. Additionally, isomerization catalysts capable of reacting with all classes of substrates are not consistently selective. Present work in the laboratory seeks to develop catalysts that are both selective for one-bond isomerization and effective towards all alkene substrates regardless of functionality. The primary complexes discussed in this work are inspired by the first series of pre-catalysts developed by Dr. J. Becica in 2018. The included phosphines were Xantphos, dppe, dppf; each resulting in Mo(CO)4(η2-R2P∩PR2) complexes. These complexes were complemented by the Mo(CO)4(PPh3)2 complex that was the cornerstone of that publication. With the improvements seen with a new pre-catalyst compared to the 2023 system, the bidentate phosphines were revisited to determine if the new system also showed improvements.

Grantor dc:publisher

Temple University. Libraries

Year dc:date.issued

2026

Author dc:creator

• Loucks, Victoria

Advisor dc:contributor.advisor

• Dobereiner, Graham

Committee members dc:contributor.committeemember

• Zdilla, Michael
• Kim, Daniel K.
• Emmert, Marion H.

• Chemistry
• Inorganic chemistry
• Organic chemistry
• Catalysis
• Isomerization

Statement dc:rights

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Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Language dc:language.iso

eng

Repository record dc:identifier.uri

https://scholarshare.temple.edu/handle/20.500.12613/12113

OAI identifier oai:identifier

oai:scholarshare.temple.edu:20.500.12613/12113