Abstract:
This thesis describes the synthesis, characterisation, and reactivity of boron porphyrin complexes and Group 14 dibenzotetramethyltetraaza[l4]annulene complexes.
Chapter 1 is a discussion of aspects of symmetry and binding modes in porphyrin chemistry. A new system of categorisation for porphyrin complexes based upon the binding mode of the porphyrin is presented.
Chapter 2 presents the synthesis and first full characterisation of a boron porphyrin B2OF2(Por) (Por=TTP (tetra-p-tolyrporphyrin), TpClPP (Tetra-p-chlorophenylporphyrin). As an introduction to this chemistry the porphyrin coordination chemistry of the other members of Group 13 is briefly discussed. Some relevant aspects of boron chemistry and the one previous literature report of a boron porphyrin are examined.
Chapter 3 describes the reactions of boron trihalides and substituted boron carriers with tetraaryl and octaethyl porphyrins, the characterisation and reactivity of their products, and the mechanisms involved. A preliminary crystal structure of B2O2(BCl3)2(TpClPP) is presented, as are the results of an AM1 semiempirical molecular orbital modelling study of some of the species observed and postulated.
Chapter 4 describes the synthetic details for those new complexes discussed in Chapter 3.
Chapter 5 describes the reactions of SnCl2, SnCl4, GeCl4, and SiCl4 with the dibenzotetramethyltetraaza[l4]annulene macrocycle (TMTAA2-) and the characterisation and reactivity of their products. The chapter is introduced by a discussion of the H2TMTAA ligand and a review of its Main Group chemistry.
Chapter 6 describes the synthetic details for those new complexes discussed in Chapter 5.