Liu, Tingting2011-07-292011-07-292011-07-29http://hdl.handle.net/2097/11012A series of chiral titanium and manganese complexes with helix-directing salen ligands have been prepared, characterized and studied. Their structures displayed as a chiral helical motif as expected. And it was also found that all M(salen) units were exclusively M-helimeric in the solid state, except Ti(cyclohexyl-benz[a]anthryl) as P-helix. This may be due to the energy difference between P and M helice, which enables crystal packing forces to control and drive the molecular structure. This is also in agreement with the previous computational studies that the M configuration predominates in THF solution. All metal centers adopt a cis-β octahedral geometry except in Mn(binapthyl-phenanthryl-salen). Most of M(salen) complexes in this work afforded μ–oxo dinuclear helicates, instead of the expected monohelicate, except Mn(binapthyl-phenanthryl-salen), which is bridged by a third salen ligand. The titanium salt affected the complex solution behavior. In the presence of Cl[superscript]-, only mononuclear species was found by ESI-MS, while both di- and mononuclear species was found in MeOH in the presence of –O[superscript]iPr. The NMR spectra of Ti(salen) indicated one major species with cis-β geometry exist in most solution, which could be monomer or dimer, except Ti(binapthyl-salen). No counterions have been found in the solid state of Mn(salen) complexes in this work, but they affected the ligand decomposition in the solution in Mn(binapthyl-phenanthryl-salen). The Mn(salen) complexes could effectively and enatioselectively catalyze the asymmetric epoxidation of somoe trans, cis and terminal olefin, and various oxidants were employed.en-US© the author. This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).http://rightsstatements.org/vocab/InC/1.0/Transition metal complexAsymmetric epoxidationDissertationChemistry (0485)Inorganic Chemistry (0488)