Diaryl Triazenides as Ligands for the Lanthanides and Related Studies

This thesis outlines the synthesis and coordination chemistry of 1,3-diaryl triazenes, inparticular, their alkali metal coordination chemistry and the utility of these complexes asprecursors to lanthanide triazenide complexes.Chapter II outlines the synthesis of the extremely sterically demanding 1,3-bis(2,6-dibenzhydryl-4-methylphenyl)triazene as well as a range of organic precursors to thistriazene. The unsuccessful attempts to synthesise the analogous formamidine throughmany and varied routes are also outlined. The synthesis of the alkali metal complexes of1,3-bis(2,6-diisopropylphenyl)triazene are described herein.Chapter III describes the synthesis of a range of lanthanide triazenides in both thetrivalent and divalent oxidation states. The utility of the common methods of synthesisof amidolanthanides to the triazenide complexes described herein is examined. Theunsuccessful attempts to synthesise a cerium(IV) triazenide are also described in thischapter. Calculations performed to numerically describe the steric congestion atlanthanide triazenides and to rationalise their reactivity relative to previously describedlanthanocenes are also outlined in this chapter.Chapter IV describes the reactivity of 2,6-dibenzhydryl-4-methyliodobenzene withcalcium and the lanthanide metals. An unusual fluorenide reaction product is identifiedwith calcium and ytterbium metal and a proposed reaction mechanism is outlined. Thisreaction outcome is compared to pre-existing arylcalcium and arylytterbium chemistry