Understanding the role of the dithiolate cofactor is key to developing new mechanistic insights and, possibly, new applications of the now famous Fe2(μ-SR)2L6 motif. Experimental results on following aspect of the dithiolate will be discussed: *(μ-SR)2 = SCH2NMeCH2S vs SCH2NHCH2S, which has a decisive effect on the reactivity of the diiron center toward air. *(μ-SR)2 = SCH2N+Me2CH2S vs SCH2NMeCH2S, which has a decisive effect on the redox properties of the FeFe center. *(μ-SR)2 = SCH2CMe2CH2S vs SCH2CH2CH2S, which has a decisive effect on behavior of terminal hydrides.

Effect of the dithiolate cofactor on the reactivity, spectroscopy, and electrochemistry of models for the [FeFe]-hydrogenases

253rd National Meeting (2017)

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