QUADRUPOLE CENTRAL TRANSITION NMR SPECTROSCOPY OF QUADRUPOLAR NUCLEI IN SOLUTION

This thesis reports on 17O (I = 5/2) and 59Co (I = 7/2) quadrupole central transition (QCT) NMR studies of three classes of biologically important molecules: glucose, nicotinamide and Vitamin B12 derivatives. Extensive QCT NMR experiments were performed over a wide range of molecular motion by changing solvent viscosity and temperature. 17O-labels were introduced at the 5- and 6-positions respectively: D-[5-17O]-glucose and D-[6-17O]-glucose following the literature method. QCT NMR greatly increased the molecular size limit obtained by ordinary solution NMR. It requires much lower temperatures to get the optimal spectral resolution, which are preferable for biological molecules. In addition, quadrupolar product parameter (PQ) and shielding anisotropy product parameter (PSA) were obtained for hydroxide group and amide group for the first time. For conventional NMR studies of quadrupolar nuclei, only PQ is accessible while QCT NMR obtained both PQ and PSA simultaneously. Our experiments also suggest the resolution of QCT NMR can be even better than that obtained by conventional NMR. We observed for the first time that the second-order quadrupolar interaction becomes a dominant relaxation mechanism under ultraslow motion. All these observations suggest that QCT NMR can become a standard technique for studying quadrupolar nuclei in solution.

The syntheses and characterization of nickel complexes; investigation of Ni(dppp)2 and [NiX(dppp)n]x, potentially catalytically active nickel(0)/(I) species for cross-coupling reactions

This thesis describes an investigation in which we compare Ni(0), Ni(I) and Ni(II) complexes containing 1,3-bis(diphenylphosphino)propane (dppp) as a phosphine ligand for their abilities to effect three types of cross-coupling reactions: Buchwald-Hartwig Amination, Heck-Mizoroki, and Suzuki-Miyaura cross-coupling reactions with different types of substrates. The Ni(0) complex Ni(dppp)2 is known and we have synthesized it via a new procedure involving zinc reduction of the known NiCl2(dppp) in the presence of an excess of dppp. The Ni(0) complex was characterized by NMR spectroscopy and X-ray crystallography. Since Ni(I) complexes of dppp seem unknown, we have synthesized what at this stage appear to be NiXdpppn/[NiX(dppp)n]x (X = Cl, Br, I; n = 1,2, x = 1, 2) by comproportionation of molar equivalents of Ni(dppp)2 and NiX2dppp, X= Cl, Br, I.