Researcher ORCID Identifier
0000-0003-4337-6246
Graduation Year
2022
Document Type
Campus Only Senior Thesis
Degree Name
Bachelor of Arts
Department
Chemistry
Reader 1
Nancy Williams
Reader 2
Mary Van Vleet
Terms of Use & License Information
Rights Information
©2022 Sarah I Meadows
Abstract
Computational studies of the two square planar, isomeric complexes, [(NCN)Pt(Me)ax(Ph)eq]+ and [(NCN)Pt(Ph)ax(Me)eq]+ have been carried out (NCN = 2,6-bis(diethylaminomethyl)phenyl, (R)ax = axial, (R)eq = equatorial). Experimentally, it has been shown that [(NCN)Pt(Me)ax(Ph)eq]+ affords the s-agostic complex [(NC(-Me)N)Pt(Ph)eq]+ in which the platinum forms a σ complex with the aryl-methyl bond. Computationally, this barrier is found to be far lower than the barrier to either toluene elimination (which requires energetically prohibitive phenyl rotation) or isomerization to [(NCN)Pt(Me)ax(Ph)eq]+. In contrast, the [(NCN)Pt(Me)ax(Ph)eq]+ shows high, similar barriers to toluene formation, aryl-phenyl coupling, and isomerization to [(NCN)Pt(Me)ax(Ph)eq]+. Experimentally, toluene formation is observed. Insights from our computations as to why the toluene pathway is the most favored will be discussed.
Recommended Citation
Meadows, Sarah, "Computational studies of competitive C-C reductive elimination from two isomeric Pt(IV) cationic complexes" (2022). Scripps Senior Theses. 1833.
https://scholarship.claremont.edu/scripps_theses/1833
This thesis is restricted to the Claremont Colleges current faculty, students, and staff.
