New Class of Diiron Dithiolates Related to the Fe-Only Hydrogenase Active Site: Synthesis and Characterization of [Fe2(SR)2(CNMe)7]2+
- 29 October 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 41 (24) , 6193-6195
- https://doi.org/10.1021/ic025919t
Abstract
Electron-rich polyisocyano derivatives Fe2(S2CnH2n)(CO)6-x(CNMe)x (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(S2C3H6)(CNMe)7](PF6)2 with excess CNMe.Keywords
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