403326-19-2Relevant academic research and scientific papers
Active-site models for iron hydrogenases: Reduction chemistry of dinuclear iron complexes
De Carcer, Inigo Aguirre,DiPasquale, Antonio,Rheingold, Arnold L.,Heinekey, D. Michael
, p. 8000 - 8002 (2006)
Reduction of Fe2(μ-S2C3H 6)(CO)6 (1) in tetrahydrofuran with 1 equiv of decamethylcobaltocene (Cp*2Co) affords a tetranuclear dianion 2. The IR spectra of samples of 2 in solution and in the solid state exhibit a band at 1736 cm-1, suggestive of the presence of a bridging carbonyl (CO) ligand. X-ray crystallography confirms that the structure of 2 consists of two Fe2 units bridged by a propanedithiolate moiety formulated as [Fe2(μ-S2C3H6)(CO) 5-(SCH2CH2CH2-μ-S)Fe 2(μ-CO)(CO)6]2-. One of the Fe2 units has a bridging CO ligand and six terminal CO ligands. The second subunit exhibits a bridging propanedithiolate moiety. One CO ligand has been replaced by a terminal thiolate ligand, replicating the basic architecture of Fe-only hydrogenases. The reduction reaction can be reversed by treatment of 2 with 2 equiv of [Cp2Fe][PF6], reforming complex 1 in near-quantitative yield. Complex 2 can also be oxidized by acids such as p-toluenesulfonic acid, regenerating complex 1 and forming H2.
Surprising Condensation Reactions of the Azadithiolate Cofactor
Zhang, Fanjun,Richers, Casseday P.,Woods, Toby J.,Rauchfuss, Thomas B.
, p. 20744 - 20747 (2021)
Azadithiolate, a cofactor found in all [FeFe]-hydrogenases, is shown to undergo acid-catalyzed rearrangement. Fe2[(SCH2)2NH](CO)6 self-condenses to give Fe6[(SCH2)3N]2(CO)17. The reaction, which is driven by loss of NH4+, illustrates the exchange of the amine group. X-ray crystallography reveals that three Fe2(SR)2(CO)x butterfly subunits interconnected by the aminotrithiolate [N(CH2S)3]3?. Mechanistic studies reveal that Fe2[(SCH2)2NR](CO)6 participate in a range of amine exchange reactions, enabling new methodologies for modifying the adt cofactor. Ru2[(SCH2)2NH](CO)6 also rearranges, but proceeds further to give derivatives with Ru-alkyl bonds Ru6[(SCH2)3N][(SCH2)2NCH2]S(CO)17 and [Ru2[(SCH2)2NCH2](CO)5]2S.
