| Abstract
| - Syntheses and ligand-substitution chemistry of monomeric thiophenoxyimine complexes of rhodium, iridium, nickel, and platinum are reported. Crystallographic and computational investigation showed that the size of the substituent on the imine carbon has a large effect on ligand conformation and coordination behavior.
- Monomeric thiosalicylaldiminate complexes of rhodium(I) and iridium(I) were prepared by ligandtransfer from the homoleptic zinc(II) species. In the presence of strongly donating ligands, the iridiumcomplexes undergo insertion of the metal into the imine carbon−hydrogen bond. Thiophenoxyketimineswere prepared by nontemplated reaction of o-mercaptoacetophenone with anilines and were complexedwith rhodium(I), iridium(I), nickel(II), and platinum(II). X-ray crystallographic studies showed that whilethe thiosalicylaldiminate complexes display planar ligand conformations, those of the thiophenoxyketiminates are strongly distorted. Results of a computational study predicted that all synthetically accessiblethiophenoxyketiminates will display distorted geometries.
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