Platinum Group Thiophenoxyimine Complexes:  Syntheses and Crystallographic/Computational Studies

Abstract

Monomeric thiosalicylaldiminate complexes of rhodium(I) and iridium(I) were prepared by ligand transfer from the homoleptic zinc(II) species. In the presence of strongly donating ligands, the iridium complexes undergo insertion of the metal into the imine carbon−hydrogen bond. Thiophenoxyketimines were prepared by nontemplated reaction of o-mercaptoacetophenone with anilines and were complexed with rhodium(I), iridium(I), nickel(II), and platinum(II). X-ray crystallographic studies showed that while the thiosalicylaldiminate complexes display planar ligand conformations, those of the thiophenoxyketiminates are strongly distorted. Results of a computational study predicted that all synthetically accessible thiophenoxyketiminates will display distorted geometries.

Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes

“…In thiophloroglucinol the C Ar SH resonance is observed at 133.0 ppm, [93] and the carbon atom of a thiocarbonyl is shifted to low field up to about 160 ppm. [95] In this compound the C Ar S resonance can be assigned to a signal at 162.2 ppm, and indeed they concluded that the thione-enamine resonance structure has a strong contribution to the overall reso- nance hybrid in this compound. [95] In this compound the C Ar S resonance can be assigned to a signal at 162.2 ppm, and indeed they concluded that the thione-enamine resonance structure has a strong contribution to the overall reso- nance hybrid in this compound.…”

NMR, MP2, and DFT study of thiophenoxyketenimines (o‐thio‐Schiff bases): Determination of the preferred form

“…The study by Corrigan et al revealed that most compounds preferred the NH form . This was also confirmed in the solid state by an X‐ray investigation by Krinsky et al for derivatives of o ‐thioacetophenones . A characteristic is the NH proton chemical shift being above 17 ppm for derivatives based on 2‐mercaptoacetophenones and p ‐anisidine or p ‐toluidine.…”

“…Compounds 2 , 3 , and 5 were prepared according to Krinski et al and compounds 1 and 4 were prepared by shaking benzene solutions of o ‐mercaptoacetophenone and o ‐mercaptobenzophenone, respectively, with an excess of methylamine solution in water. In the latter case, the target compound was precipitated and was purified by filtration of the solution through a plug of neutral alumina.…”

“…Derivatives based on o ‐thioaldehydes have a tendency to rearrange into dithiocins and are usually not isolated as pure compounds. A couple of derivatives based on 2‐mercaptoacetophenones and p ‐anisidine or p ‐toluidine have been synthesized and characterized partly by nuclear magnetic resonance (NMR) and by X‐ray crystallography . In this study, derivatives based on 2‐thioacetophenone and 2‐thiobenzophenone are synthesized with aliphatic, benzylic, and aromatic substituents at nitrogen (see Scheme ).…”

Subkomponenten‐Selbstorganisation und Transmetallierung zweikerniger Helikate

“…[8,9] Die Transmetallierung von supramolekularen Strukturen, die durch klassische oder durch Subkomponenten-Selbstorganisation erhalten wurden, stellt eine vielversprechende Strategie dar, um die genannten Defizite zu überwinden. Dieser Strategie folgend, können supramolekulare Strukturen mit Liganden, die nicht durch klassische organische Synthese zugänglich sind, durch Subkomponenten-Selbstorganisation erhalten werden, und diese Liganden können anschließend durch Transmetallierung in klassischen supramolekularen Prozessen genutzt werden.…”