Probing the reactivity and radical nature of oxidized transition metal-thiolate complexes by mass spectrometry

Transition metal thiolate complexes such as [PPN]⁺[RuL ₃]^- (PPN = bis(triphenylphosphoranylidene) ammonium and L = diphenylphosphinobenzenethiolate) are known to undergo addition reactions with unsaturated hydrocarbons via the formation of new C-S bonds in solution upon oxidation. The reaction mechanism is proposed to involve metal-stabilized thiyl radical intermediates, a new type of distonic ions such as [RuL ₃]⁺ ion in the case of [PPN]⁺[RuL ₃]^-. This study presents the reactivity and structure investigation of [RuL₃]⁺ by mass spectrometry (MS) in conjunction with ion/molecule reactions. The addition reactions of [RuL ₃]⁺ with alkenes or methyl ketones in the gas phase are indeed observed, in agreement with the proposed mechanism. Such reactivity is also maintained by several fragment ions of [RuL₃]⁺, indicating the preserved thiyl diradical core structure is responsible for the addition reaction. The thiyl radical nature of [RuL₃]⁺ was further verified by the ion/molecule reaction of [RuL₃]⁺ with dimethyl disulfide, in which the characteristic CH₃S• transfer occurs, both at atmospheric pressure and also at low pressure (~mTorr). These results provide, for the first time, clear mass spectrometric evidence of the radical nature of [RuL₃]⁺ (i.e.; the distonic ion structure of [RuL₃]⁺), arising from the oxidation of non-innocent thiolate ligands of the complex [PPN]⁺[RuL ₃]^-. Similar thiolate complexes, including ReL₃ and NiL₂, were also examined. Although reactions of oxidized ReL₃ or NiL₂ with CH₃SSCH₃ take place at atmospheric pressure, the corresponding reaction did not occur in vacuum. Consistent with these data, the addition of ethylene was not observed either, indicating lower reactivities of [ReL₃]⁺ and [NiL₂]⁺ in comparison to [RuL₃]⁺. [Figure not available: see fulltext.]