Terminal Hydride in [FeFe]-Hydrogenase Model Has Lower Potential for H2 Production Than the Isomeric Bridging Hydride
- 12 March 2008
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 47 (7), 2261-2263
- https://doi.org/10.1021/ic800030y
Abstract
Protonation of the symmetrical tetraphosphine complexes Fe2(S2CnH2n)(CO)2(dppv)2 afforded the corresponding terminal hydrides, establishing that even symmetrical diiron(I) dithiolates undergo protonation at terminal sites. The terminal hydride [HFe2(S2C3H6)(CO)2(dppv)2]+ was found to catalyze proton reduction at potentials 200 mV milder than the isomeric bridging hydride, thereby establishing a thermodynamic advantage for catalysis operating via terminal hydride. The azadithiolate protonates to afford, [Fe2[(SCH2)2NH2](CO)2(dppv)2]+, [HFe2[(SCH2)2NH](CO)2(dppv)2]+, and [HFe2[(SCH2)2NH2](CO)2(dppv)2]2+, depending on conditions.Keywords
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