Synthesis, Structure and Reactivity of Pincer Supported Nickel Carbenes and Related Complexes

Simple item page
dc.contributor.advisorPiers, Warren E.
dc.contributor.authorLaPierre, Etienne Alain
dc.contributor.committeememberBaumgartner, Thomas
dc.contributor.committeememberRoesler, Roland
dc.contributor.committeememberPonnurangam, Sathish
dc.contributor.committeememberJohnson, Samuel A.
dc.date2019-06
dc.date.accessioned2018-11-14T19:12:12Z
dc.date.available2018-11-14T19:12:12Z
dc.date.issued2018-11-13
dc.description.abstractThe activation of abundant or renewable feedstocks such as H2O, O2, CH4, CO2, N2 and NH3 and the development of sustainable systems for their productive conversion to value-added products are necessary to meet the growing demand for chemical and energy products. Complicating this are the unique challenges presented by these substrates and the current reliance on expensive and sparse 2nd and 3rd row transition metals to effect these bond activations. This work centres on the further development of nickel carbene complexes as a platform for small molecule activation. These species had been previously demonstrated to heterolytically activate numerous acidic bonds, including the weakly acidic bonds of ammonia. The landscape of bond activations has been expanded beyond acidic substrates to include hydridic, industrially important silanes, coupled with detailed mechanistic studies. Insights gleaned through these studies allowed for rational ligand modifications to improve stability, facilitating the study of CO2 and CO activation, and the synthesis of an umpolung cationic nickel carbene. The polarity reversal of the Ni-C moiety resulted in reactivity distinct from its neutral analogue, as exemplified by the unique ligand centred activation of ammonia. Further, preliminary studies suggest these reverse-polarity carbenes may be competent in catalytic hydrodefluorination of alkyl fluorides, an important first step in moving Ni carbenes from academic curiosity to application. Preliminary work on the synthesis of isostructural Pt carbenes will also be presented, allowing for a comparison of the bonding and reactivity in group 10 carbenes.en_US
dc.identifier.citationLaPierre, E. A. (2018). Synthesis, Structure and Reactivity of Pincer Supported Nickel Carbenes and Related Complexes (Doctoral thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca. doi:10.11575/PRISM/34229en_US
dc.identifier.doihttp://dx.doi.org/10.11575/PRISM/34229
dc.identifier.urihttp://hdl.handle.net/1880/109173
dc.language.isoeng
dc.publisher.facultyGraduate Studies
dc.publisher.facultyScience
dc.publisher.institutionUniversity of Calgaryen
dc.publisher.placeCalgaryen
dc.rightsUniversity of Calgary graduate students retain copyright ownership and moral rights for their thesis. You may use this material in any way that is permitted by the Copyright Act or through licensing that has been assigned to the document. For uses that are not allowable under copyright legislation or licensing, you are required to seek permission.
dc.subjectOrganometallic
dc.subjectNickel
dc.subjectPCP
dc.subjectCarbene
dc.subjectSmall Molecule Activation
dc.subject.classificationChemistry--Inorganicen_US
dc.titleSynthesis, Structure and Reactivity of Pincer Supported Nickel Carbenes and Related Complexes
dc.typedoctoral thesis
thesis.degree.disciplineChemistry
thesis.degree.grantorUniversity of Calgary
thesis.degree.nameDoctor of Philosophy (PhD)
ucalgary.item.requestcopytrue
Files
Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
ucalgary_2018_lapierre_etienne.pdf
Size:
61.99 MB
Format:
Adobe Portable Document Format
Description:
Full Thesis
Download
License bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
license.txt
Size:
1.74 KB
Format:
Item-specific license agreed upon to submission
Description:
Download
Collections
Open Theses and Dissertations