This dissertation focuses on the use of benzimidazole compounds as ligand for transition metals. Studies are focused on the benzimidazole as a ligand through its pyridine type nitrogen atom, but also properties associated with the steric bulk of the arene ring. In addition, second coordination sphere interactions will be explored in cases of benzimidazole compounds modified with hydrogen bonding groups in close proximity to the benzimidazole binding moiety. The ligands bis(benzimidazol-2-ylmethypamine and bis(1-methylbenzimidazol-2-ylmethyl)amine are shown to bind to transition metals through three nitrogen atoms, with stability constants ranging from 4.5 x 10 5 to 2.1 x 10 11 L/mol. Both ligands have the highest stability constant with Cu2+ , compared to Zn2+ , Ni2+ , and Co2+ . Also, the ligands tend to resist bis-chelation. Crystal structures of Z2+ and Ni2+ complexes of 2-amino-l-methylbenzimidazole show two ligands bind per metal ion when reacted with acetate salts, and the exocyclic nitrogen can engage in hydrogen bonding. In the Zn2+ complex, there is no evidence of internal hydrogen bonding in the solid state, but the Ni2+ complex show internal hydrogen bonding to the bound acetate ions, similar to the previously reported Cu2+ complex with 2-amino-1-methylbenzimidazole. The ligand 2,2-dimethyl-N-(1-methylbenzimidazol-2-yl)propionamide (Hdmmbp) shows tautomeric and acidic properties, where the ligand exists primarily as an imide with the hydrogen on the benzimidazole nitrogen. In the solution state, there is a rapid transition between two tautomeric forms. In the solid state, there is a chain of hydrogen bonding interactions between the benzimidazole nitrogen and the carbonyl oxygen of a neighboring molecule. Calculations show that the hydrogen can be transferred between molecules, with an energy of 29.078 kJ/mol. The ligand Hdmmbp coordinates to Cu2+ , Zn2+ , Ni2+ , and Co 2+ , generally as an anion, bis-chelated through the benzimidazole nitrogen and the carbonyl oxygen, creating a four-coordinate complex. The Ni(dmmbp) 2 complex can expand its coordination sphere to five-coordinate with some ligands and solvents. The ligand Hddmbp, when complexed with Pt2+ , can be in the form of a bis-ligated amide or a bis-chelated amido complex, similar to the complexes for Cu2+ , Zn2+ , Ni2+ , and Co2+ . Complexes can be interchanged between the two by changing pH conditions. Complexes similar in structure to cisplatin can be synthesized using this ligand, and these complexes have been shown to have cytotoxic properties.