Fluorinated‐Thiolate Osmium(III) and Osmium(IV) Complexes Bearing N,N‐diethyldithiocarbamate and Substituted Phosphines. Synthesis, Crystal Structures and DFT‐Studies

The paramagnetic osmium(III) [Os(SR F )(S 2 CNEt 2 ) 2 (P(C 6 H 4 X‐4) 3 )] (R F =C 6 F 4 H−4, C 6 F 5 ; X=OCH 3 , CH 3 , F) ( 1–6 ) along with diamagnetic osmium(IV) [Os(SR F ) 2 (S 2 CNEt 2 ) 2 ] ( 7–8 ) complexes were obtained from [Os(SR F ) 4 (P(C 6 H 4 ‐X) 3 )] and NaS 2 CNEt 2 , which were characterized by FAB mass spectrometry, IR spectroscopy, single crystal X‐ray diffraction, and for the diamagnetic 7 also by NMR. TD‐DFT calculations were performed to simulate the absorption spectra of complexes. In the visible region, LMCT transitions contribute to the calculated intensities, which are somewhat related to the color of the synthesized compounds. In the ultraviolet region, the phosphine ligand plays a significant role in MLCT transitions, which results in Os(III) complexes exhibiting an intense band in that region. Topological analysis and electron localization function (ELF) maps calculated for 6 and 7 confirm the strong ionic character of the Os−S coordination bonds formed by the thiophenolate and dithiocarbamate ligands. This comprehensive study provides information on the structure, bonding, and electronic properties of osmium complexes, for potential applications in catalysis, materials science, and biological systems.