American Chemical Society
ic025838x_si_002.cif (15.53 kB)

Bimetallic Carbonyl Thiolates as Functional Models for Fe-Only Hydrogenases

Download (15.53 kB)
posted on 2002-11-15, 00:00 authored by Frédéric Gloaguen, Joshua D. Lawrence, Thomas B. Rauchfuss, Marc Bénard, Marie-Madeleine Rohmer
The anion [Fe2(S2C3H6)(CN)(CO)4(PMe3)]- (2-) is protonated by sulfuric or toluenesulfonic acid to give HFe2(S2C3H6)(CN)(CO)4(PMe3) (2H), the structure of which has the hydride bridging the Fe atoms with the PMe3 and CN- trans to the same sulfur atom. 1H, 13C, and 31P NMR spectroscopy revealed that HFe2(S2C3H6)(CN)(CO)4(PMe3) is stereochemically rigid on the NMR time scale with four inequivalent carbonyl ligands. Treatment of 2- with (Me3O)BF4 gave Fe2(S2C3H6)(CNMe)(CO)4(PMe3) (2Me). The Et4NCN-induced reaction of Fe2(S2C3H6)(CO)6 with P(OMe)3 gave {Fe2(S2C3H6)(CN)(CO)4[P(OMe)3]}- (4). Spectroscopic and electrochemical measurements indicate that 2H can be further protonated at nitrogen to give [HFe2(S2C3H6)(CNH)(CO)4(PMe3)]+ (2H2+). Electrochemical and analytical data show that reduction of 2H2+ gives H2 and 2-. Parallel electrochemical studies on [HFe2(S2C3H6)(CO)4(PMe3)2]+ (3H+) in acidic solutions led also to catalytic proton reduction. The 3H+/3H couple is reversible, whereas the 2H2+/2H2 couple is not, because of the efficiency of the latter as a proton reduction catalyst. Proton reduction is proposed to involve protonation of reduced diiron hydrides. DFT calculations establish that the regiochemistry of protonation is subtly dependent on the coligands but is more favorable to occur at the Fe−Fe bond for [Fe2(S2C3H6)(CN)(CO)4(PMe3)]- than for [Fe2(S2C3H6)(CN)(CO)4(PH3)]- or {Fe2(S2C3H6)(CN)(CO)4[P(OMe)3]}-. The Fe2H unit stabilizes the conformer with eclipsed CN and PMe3 because of an attractive electrostatic interaction between these ligands.