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论文类型：期刊论文

发表时间：2018-09-24

发表刊物：ORGANOMETALLICS

收录刊物：SCIE

卷号：37

期号：18

页面范围：3165-3173

ISSN号：0276-7333

摘要：The sulfur-based reactivity of transition-metal thiolate complexes toward alkenes has received extensive attention as a significant proposal for a potential olefin purification scheme. The one-electron oxidation of half sandwich iron thioether-dithiolate complex [Cp*Fe(eta(3)-tpdt)] (1, Cp* = eta(5)-C5Me5; tpdt = S(CH2CH2S-)(2)) resulted in the formation of iron-stabilized thiyl radicals, which can interact with unsaturated hydrocarbons such as alkenes or alkynes to give the corresponding trithioether-iron adducts. Interestingly, during this transformation process, the formal oxidation state of the iron center changed from +IV to +II, which suggests a two-electron transfer from unsaturated hydrocarbons to the iron center. Furthermore, the electrochemical measurements reveal this C-S bond formation is an irreversible process, during which ethylene cannot release under electrochemical reductive conditions. These adducts were unambiguously identified by various spectroscopic and X-ray crystallographic characterizations.