New nickel complexes with an S 4 coordination sphere; synthesis, characterization and reactivity towards nickel and iron compounds

Abstract

Three new nickel complexes have been synthesized with the ligands Hbss (4-mercapto-2-thia-1-butylbenzene) and Hbsms (2-(benzylsulfanyl)-2-methyl-1-propanethiol). [Ni(bss) 2] is a mononuclear complex with an S 4 coordination environment. [Ni 3(bss) 4](BF 4) 2 and [Ni 3(bsms) 4](BF 4) 2 are linear trinuclear complexes that can be synthesized either directly from the ligands Hbss and Hbsms in a reaction with Ni(BF 4) 2, or via the mononuclear complexes [Ni(bss) 2] and [Ni(bsms) 2] in a reaction with Ni(BF 4) 2. These reactions have been monitored with ligand field spectroscopy. Crystals suitable for X-ray diffraction were obtained for [Ni 3(bss) 4](BF 4) 2. The complex crystallizes in the space group P2 1/ c. The nickel centers are in a square-planar environment; two peripheral nickel centers with an S 2S 2 ′ (S=thiolato; S ′=thioether) coordination environment and the central nickel ion with an S 4 coordination environment. The mononuclear nickel complexes [Ni(bss) 2] and [Ni(bsms) 2] were reacted with FeCl 2, resulting in the hetero-tetranuclear nickel–iron complexes [Ni(bss) 2FeCl 2] 2 and [Ni(bsms) 2FeCl 2] 2. All complexes were characterized by analytical and spectroscopic methods.