Electron-rich polyisocyano derivatives Fe2(S2CnH2n) (CO)6-χ(CNMe)χ (x ∼ 4) undergo oxidatively induced (FeCp2+) reaction with additional CNMe to give [Fe2(SR)2(CNMe)7] (PF6)2, a new class of iron thiolates. Crystallographic characterization established that the 34 e- dinuclear core resembles the oxidized (H2-binding) form of the active sites of the Fe-only hydrogenases, key features being the face-sharing bioctahedral geometry, the μ-CX ligand, and an Fe-Fe separation of 2.61 Å. Oxidation of the phenylthiolate Fe2(SPh)2(CO)2(CNMe)4 led to mononuclear [Fe(SPh)(CNMe)5]-(PF6), which is analogous to [Fe2(SR)2(CNMe)10] (PF6)2 formed upon treatment of [Fe2(S2C3He)(CNMe)7] (PF6)2 with excess CNMe.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry