Synthesis and characterisation of tetracyclic guanidinium phase transfer catalysts I and II from ethyl (R)-3-hydroxybutyrate was undertaken as well as the determination of their pKa's to provide insight into the mechanism of their use in phase transfer catalysis. Their proficiency at catalysing the Michael addition of 2-hydroxy-1 ,4-napthaquinone III to trans-β-nitrostyrene IV was studied. Catalyst II showing improved reaction times and e.e. 's over I. The synthesis of tetracyclic guanidinium salt V was also attempted unsuccessfully.
Synthesis of copper (I) hydride (CuH.X, X = H₂0 and pyridine) from three different routes (Wilrtz Reaction [1], NaBH₄ reduction [2] LiAlH₄ reduction in pyridine [3]) and their subsequent investigation by inelastic neutron scattering (INS) techniques (neutron diffraction/spectroscopy) and X-Ray diffraction (XRD) provided insight into the structure of the copper hydride core and also the nature of the stabilising surface shell (H₂0 and pyridine respectively). Direct synthesis of Stryker 's reagent [HCu{P(C6H5) 3}]6 from copper (11)
acetate (Cu(OAc)2) and also its deuterium analogues [DCu{P(C₆H₅)₃}]₆ and
[HCu{P(C₆D₅)₃} ]₆ were achieved and the location of their hydride ligands using INS (SANDALS - neutron diffraction) was determined.
Synthesis of organometallic bis-(η³-π-ally1)M (M = Ni VI & Pd VII) cross-coupling catalysts from the Grignard reaction of metal halides and preparation of active Ni-terpyridyl complexes (general formula LNil₂, L = TPY) VIII - XI from the reaction ofNi(COD)₂ and I₂ with the starting material TPY's was achieved and vibrational INS spectra (TOSCA - neutron spectroscopy) was used to investigate the low energy vibrations which are linked to catalytic activity. Similar studies were performed on the commercially available Pd stabilised NHC PEPPSI pre-catalysts (IPr XII and IMes XIII)).