My M. Phil program is on the studies of chemistry using theoretical ab initio quantum mechanical computational approach. I have focused on two subjects, which are the porphyrin analogs and decompositions of transition metal-alkyl complexes. ⁰ _{x 3 y 3 z}...[ Read more ]

My M. Phil program is on the studies of chemistry using theoretical ab initio quantum mechanical computational approach. I have focused on two subjects, which are the porphyrin analogs and decompositions of transition metal-alkyl complexes.

In Chapter 1, the decomposition reactions of d⁰ metal-alkyls in Groups IVB, VB and VIB are studied. In Chapter 2, the substituent effects on the decomposition reactions of Group VB complexes of type MCl_x(CH₃)_y(SiH₃)_z are investigated. Together, they provided much theoretical insights in the mechanistic and geometrical area. The mode of elimination in transition metal-alkyls is predicted and the preference of silane elimination over methane elimination is explained.

After an introductory note on porphyrin chemistry in Chapter 3, results from theoretical calculations on porphyrin analogs are presented in Chapters 4-6. In Chapter 4, the eight porphyrin isomers are studied, focusing on areas such as geometries, relative stabilities, electronic structures and tautomerizations. In Chapter 5, a class of "expanded porphryin" known as dibenzoporphycene has shown interesting geometrical and electronic features. Our results clearly reveal the origins of these features. In Chapter 6, isomers of shrinked porphyrin are under investigation with regard to their relative stabilities and electronic structures. In addition, the copper and nickel complexes of corrole are studied and their electronic structures predicted.