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Title: | SYNTHESIS OF TRANSITION METAL PCCARBENEP PINCER COMPLEXES AND THEIR APPLICATIONS | Authors: | WANG QINGYANG | Keywords: | transition metal,carbene,synthesis,catalysis,reactivity | Issue Date: | 7-Jan-2020 | Citation: | WANG QINGYANG (2020-01-07). SYNTHESIS OF TRANSITION METAL PCCARBENEP PINCER COMPLEXES AND THEIR APPLICATIONS. ScholarBank@NUS Repository. | Abstract: | Transition metal pincer chemistry is an established foundation in modern organometallic chemistry. However, PCcarbeneP pincer frameworks, featuring central alkylidene donors, are still relatively rare and unexplored. In 2013, Piers and co-workers reported a novel metal-ligand cooperative concept with a nickel PCcarbeneP complex to activate a series of small molecules. Inspired by his work, the thesis explores the synthesis of base metal (Fe and Co) PCcarbeneP complexes using the latest dehydration approach. This represents the first examples of iron and cobalt PCcarbeneP complexes. Additionally, unique reactivity between previously reported rhodium PCcarbeneP pincer complexes and alkynes to generate a series of rhodium allyl complexes is explored. The rhodium allyl complexes were found to be effective in hydrosilylation of alkynes.The mechanistic cycle for the catalytic hydrosilylation of alkynes using the rhodium allyl complexes and the mechanism for the formation of these complexes are explored by kinetic experiments and DFT studies. | URI: | https://scholarbank.nus.edu.sg/handle/10635/171593 |
Appears in Collections: | Ph.D Theses (Open) |
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