Two tris-chelate complexes of cobalt and rhodium and two complexes of Ru(II) of dithiocarbamate, [SCNH], were synthesized. The complexes were spectroscopically characterized by IR, NMR, UV-vis, and MS and structurally characterized by X-ray diffraction. The structural features of the rhodium complex were compared to those of other tris-chelate Rh(III) dithiocarbamate complexes and are characterized by a change in the ground-state geometry in comparison to expected octahedral tris-chelate complexes. This was confirmed both experimentally by X-ray diffraction and theoretically using DFT calculations. The inversion barriers of Rh(Bzdtc), Ir(Bzdtc), and Rh(Etdtc) were determined using VT-NMR in DMSO. These barriers were found to be surprisingly low for heavy group 9 elements of d tris-chelate complexes: values of 16.7, 17.1, and 16.4 kcal/mol were calculated, respectively. By comparing structural features, we are able to determine that the activation barrier for the inversion of stereochemistry of Rh(Hdtc) must have a similarly low value. A modified version of the Bailar twist involving an intermediate with geometry was proposed as the mechanism of inversion.
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