The reactions of M(CO)5(S) (M= Cr or W, S= solvent) with a senes of ligands, L, (L= dumine), were investigated In each case the appropnate chelate M(CO)4(L) compounds were formed The intermediates, M(CO)5(L), were also isolated and characterised by infrared, UV-visible and 'H n m r spectroscopy. The activation parameters for the formauon of the M(CO)4(L) species were determined, where possible. The subsequent reactions of the M(CO)5(L) intermediates were investigated and a mechanism for the chelate formation is proposed W(CO)5(2 ,2 '- bipyndylamine) was synthesised and structurally characterised by single crystal X-ray diffraction as a model for the monodentately coordinated dumine compounds. An investigation into the effect of conformational change on the pKa of the conjugate acid of 2,2'-bipyndine and related ligands was also conducted. Complete neglect of differential overlap (CNDO) calculations revealed that, for non-polar media, there was an increase in pKa of the conjugate acid of 2,2'-bipyndine when the angle (0) between the pyndine nngs was in the range 105-120°. In polar media the pKa of the conjugate acid of 2,2'-bipyndine was at a maximum when the ligand adopted the cis conformation (0= 0°). This study was also extended to include the conjugate acid of the dimethyldumine ligand. The results showed that, for non-polar media, there was an increase in the pKa of the conjugate acid of the dimethyldumine ligand when the angle between the two nitrogens was in the range of 90-105°. In polar media this angle was revealed to be in the range of 75-105°.