Physical Sciences and Mathematics Commons^™

Structural Analysis Of [Ni(Dippe)] Fragment Using Computational Methods, Jennifer L. Sanchez

Theses and Dissertations

The structural analysis of the Nickel (Bisdiisopropylphospino)ethane, also known as [Ni(dippe)H]2, has been heavily studied in our group in collaboration with William D. Jones's group. A computational analysis of the [Ni(dippe)] fragment was performed to determine the structural relationship between the nickel center and its phosphine ligand, due to phosphines having both electronic and steric properties. The reactivity of the Nickel will be most dependent on the dippe ligand. A conformational search generated 244 conformers after a thorough minimization using Molecular Mechanic (MM) calculations where a thorough minimization was performed and then re-minimized using a SEED command until unique conformers …

Investigation Of The C—Cn Bond Activation Of Fluorinated Benzonitriles With [Ni(Dmpe)] And Dft Benchmarking Study With [Ni(Dippe)], Dominique C. Gallegos

Theses and Dissertations

Carbon-carbon bond activation has become a rapidly growing area of research due to its extensive range of applications. Despite the significant progress that has been made in this field, the cleavage of kinetically inert and thermodynamically stable C—C σ-bonds under mild homogeneous conditions remains a challenge. The activation is primarily limited to systems in which either relief of strain or aromatization serves as a driving force. A notable exception to this is the oxidative addition of unstrained C—CN bonds of nitriles. In this study, we are looking at the effect of fluoro substituents. We hypothesized …

Conformational Analysis Of A Taddol-Based Phosphoramidite P,N Ligand In A Palladium(Ii) Η3-Π-Allyl Complex, Tülay A. Ateşin, Abdurrahman Atesin, Oscar Rodriguez, Diego Rivera, Lohany Y. Garcia

Chemistry Faculty Publications and Presentations

Highlights

• Two lowest energy conformers differ in allyl conformation, conformer with exo allyl having lower energy.

• Lowest energy conformer has “chair” conformation of 7-membered ring and “edge-on/face-on/face-on/edge-on” array of pH groups.

• Next lowest energy conformer with exo allyl has alternating “edge-on/face-on” arrangement and “twist” 7-membered ring.

• Changes in “chair/twist” conformations with different substrates is possible due to 2.4 kcal/mol energy difference.

• These results explain stereochemical outcome of the reaction, and will guide design of new catalysts.

Abstract

The most stable conformations of a TADDOL-based phosphoramidite P,N ligand coordinated to a palladium(II) η3-π-allyl fragment have been investigated using …