Reaction of a polydentate cysteine-based ligand and its nickel(ii) complex with electrophilic and nucleophilic methyl-transfer reagents – from S-methylation to acetyl coenzyme A synthase reactivity

Abstract

The L-cysteine derived N₂S₂ ligand precursor H₂L and its nickel(II) complex L₂Ni₂ were investigated with respect to their behaviour in contact with electrophilic and nucleophilic methylation reagents (H₂L = (N,N′-dimethyl-(2R,5R)-bis-(sulfanylmethyl)-piperazine). Treatment of deprotonated L²⁻ with MeI led to the selective methylation of the thiolate groups thus generating a novel potential ligand, Me₂L, which is neutral and contains two thioether donors. The coordinating properties of Me₂L were demonstrated by the synthesis of a first nickel(II) complex: reaction with NiBr₂ led to a mononuclear complex 2 where all donor atoms coordinate to the nickel ion, which completes its octahedral coordination sphere by the two bromide ligands. If, however, the complex [LNi]₂ (1) is treated with MeI only one thiolate function per ligand moiety is methylated, while the other one remains a thiolate. This leads to [MeLNi]⁺ complex metal fragments, which trimerize including a μ₃-bridging iodide ion to give the compound 3 that was tested with regards to ACS reactivity. While it behaved inert towards CO, attempts to replace the bridging iodide ligand by methyl units in reactions with nucleophilic methylation reagents led to a product, which could not be identified but reacted with CO. Work-up showed that this protocol had converted the thiolate function of MeL⁻ into a thioester function, which corresponds to an ACS-like reactivity.