A series of novel, mixed donor amino/imino ligands have been synthesised in high yield and converted to the corresponding lithium amido/imino compounds. Both the amino/imino and the lithium amido/imino compounds were reacted with Group 4 metal complexes to give amido/imino and related complexes of Ti and Zr. Early transition metal complexes of a phenoxyimine ligand were prepared using both aminolysis and salt elimination methodologies. A series of novel diamido-ether ligands were prepared based on a xanthene or dibenzofuran framework, and several Ti complexes were prepared. The silylamino/imino compounds 2-[CyN=C(CH₃)]C₆H₄N(H)(SiMe₃)(L^TMSH) and 2-[CyN=C(CH₃)]C₆H₄N(H)(SiMe₂Bu^t)(L^TBDMSH) were synthesised in high yields by reaction of 2-[CyN=C(CH₃)]C₆H₄N(H)Li with Me₃SiC1 and Bu^tMe₂SiC1 respectively. The arylamino/imino compounds 2-[CyN=C(CH₃)]C₆H₄N(H)(xyl) (L^xylH) and 2-[CyN=C(CH₃)]C₆H₄N(H)(mes) (L^mesH) were prepared in high yields by Buchwald-Hartwig amination of the arylbromides with 2-[CyN=C(CH₃)]C₆H₄NH₂. The amino/imino ligands were deprotonated with BuⁿLi to yield the respective lithium amido/imino complexes (LLi).