Density functional theory computation of Nuclear Magnetic Resonance parameters in light and heavy nuclei.

摘要

This thesis illustrates the utilization of Density functional theory (DFT) in calculations of gas and solution phase Nuclear Magnetic Resonance (NMR) properties of light and heavy nuclei. Computing NMR properties is still a challenge and there are many unknown factors that are still being explored. For instance, influence of hydrogen-bonding; thermal motion; vibration; rotation and solvent effects. In one of the theoretical studies of 195Pt NMR chemical shift in cisplatin and its derivatives illustrated in Chapter 2 and 3 of this thesis. The importance of representing explicit solvent molecules explicitly around the Pt center in cisplatin complexes was outlined. In the same complexes, solvent effect contributed about half of the J(Pt-N) coupling constant. Indicating the significance of considering the surrounding solvent molecules in elucidating the NMR measurements of cisplatin binding to DNA. In chapter 4, we explore the Spin-Orbit (SO) effects on the 29Si and 13C chemical shifts induced by surrounding metal and ligands. The unusual Ni, Pd, Pt trends in SO effects to the 29Si in metallasilatrane complexes X-Si-(mu-mt)4-M-Y was interpreted based on electronic and relativistic effects rather than by structural differences between the complexes. In addition, we develop a non-linear model for predicting NMR SO effects in a series of organics bonded to heavy nuclei halides. In chapter 5, we extend the idea of "Chemist's orbitals" LMO analysis to the quantum chemical proton NMR computation of systems with internal resonance-assisted hydrogen bonds. Consequently, we explicitly link the relationship between the NMR parameters related to H-bonded systems and intuitive picture of a chemical bond from quantum calculations. The analysis shows how NMR signatures characteristic of H-bond can be explained by local bonding and electron delocalization concepts. One shortcoming of some of the anti-cancer agents like cisplatin is that they are toxic and researchers are looking for competitive alternatives. In Chapter 6, we illustrate the computation of NMR parameters for a set of non-toxic anti-tumor promising compounds. This Pt-azido complexes are known to be photoactivatable and the azido (N3--) ligand has interesting 15N NMR signature. In this study, we performed a localized molecular orbital analysis of nitrogen EFG and chemical shifts to explain the observed experimental trends, particularly which bonds and bond characteristics of the azido complexes is responsible for the particularly high Nbeta chemical shift and small J-coupling constants.