The tripodal ligands hydrotris(N-ethyl-2-mercaptoimidazol-1-yl)borate (NaTmEt) (1) and hydrotris(N-benzyl-2mercaptoimidazol-1-yl)borate (NaTmBn) (2), analogues of the hydrotris(N-methyl-2-mercaptoimidazol-1 -yl)borate ligand (Tm) containing alternative nitrogen substituents, have been employed to examine the racemization of their C-3 symmetric complexes with both four- and six-coordinate metals. The ligands react at room temperature with metal halides to provide C-3-symmetric metal complexes. The syntheses of the four-coordinate complexes [(TmZnCl)-Zn-Et] (3), [(TmCdBr)-Cd-Et] (4), [(TmHgCl)-Hg-Et] (5), [(TmCuPPh3)-Cu-Et] (6), [(TmAgPPh3)-Ag-Et] (7), and [(TmZnCl)-Zn-Bn] (8) are reported. The six-coordinate complexes [(TmRu)-Ru-Et(p-cymene)]Cl (9), [(TmRu)-Ru-Et(p-cymene)]PF6 (10), and [(TmMn)-Mn-Et(CO)(3)] (11) were also synthesized. The X-ray crystal structures of 3, 4, 6, and 9 are reported. The diastereotopic nature of the ethyl and benzyl hydrogen atoms in the ligands allows the enantiomeric forms of these complexes to be distinguished by H-1 NMR spectroscopy. Variable-temperature (VT) 1H NMR spectra have thus been used to investigate the energies of the racemization processes occurring in these chiral complexes. In solvents the activation energies to racemization for the four-coordinate complexes lay in the range of 53-77 kJ mol(-1). In non-donor solvents the energies are reduced and a dissociative mechanism is therefore implicated. No interconversion could be observed by VT NMR for the six-coordinate complexes in any solvent. To further explore the racemization mechanisms ab initio density functional theory calculations have been conducted on the ground- and transition-state structures of representative six-coordinate [Mn(I)] and four-coordinate [Zn(II)] complexes following a proposed nondissociative mechanism of racemization. The calculated energy barriers to racemization are 163 and 121 U mol-1, respectively. It is concluded that the low-energy racemization of substitution-labile four-coordinate complexes occurs via a dissociative mechanism, while substitution-inert six-coordinate complexes experience a significantly higher barrier to racemization. Whether this is due to the operation of a dissociative mechanism with a higher activation barrier or to a nondissociative mechanism remains unknown.