Ligand-Based Reactivity of Oxygenation and Alkylation in Cobalt Complexes Binding with (Thiolato)phosphine...

In our efforts to understand the nature of metal thiolates, we have explored the chemistry of cobalt ion supported by (thiolato)phosphine ligand derivatives. Herein, we synthesized and characterized a square-planar Co^II complex binding with a bidentate (thiolato)phosphine ligand, Co(PS1″)₂ (1) ([PS1″]^- = [P(Ph)₂(C₆H₃-3-SiMe₃-2-S)]^-). The complex activates O₂ to form a ligand-based oxygenation product, Co(OPS1″)₂ (2) ([OPS1″]^- = [PO(Ph)₂(C₆H₃-3-SiMe₃-2-S)]^-). In addition, an octahedral Co^III complex with a tridentate bis(thiolato)phosphine ligand, [NEt₄][Co(PS2*)₂] (3) ([PS2*]^2- = [P(Ph)(C₆H₃-3-Ph-2-S)₂]^2-), was obtained. Compound 3 cleaves the C-Cl bond in dichloromethane via an S-based nucleophilic attack to generate a chloromethyl thioether group. Two isomeric products, [Co(PS2*)(PSS^CH*)] (4 and 4') ([PSS^CH*]^- = [P(Ph)(C₆H₃-3-Ph-2-S)(C₆H₃-3-Ph-2-SCH₂Cl)]^-), were isolated and fully characterized. Both transformations, oxygenation of a Co^II-bound phosphine donor in 1 and alkylation of a Co^III-bound thiolate in 3, were monitored by spectroscopic methods. These reaction products were isolated and fully characterized. Density functional theory (DFT, the B3LYP functional) calculations were performed to understand the electronic structure of 1 as well as the pathway of its transformation to 2.