Mono- and Dinuclear Carbonyl Dithiolene Complexes Related to the [FeFe]-Hydrogenases

Abstract

The di-iron carbonyl dithiolene bridged complex [Fe2(CO)6(µ-S2C2(CO2Me)2)] (1) reacts with 1 equivalent of phosphane PR3 (R = Ph, OMe) to give, as major products, monosubstituted derivatives [Fe2(CO)5L(µ-S2C2(CO2Me)2)] (L = PPh3 (2), P(OMe)3 (3)). In the presence of an excess (3–4 equiv.) of P(OMe)3, the cleavage of 1 arises partly and a mixture of the mononuclear species [Fe(CO)(P(OMe)3)2(κ2-S2C2(CO2Me)2)] (4) and 3 is obtained. The compounds 2–4 were analyzed by IR and 1H, 31P-{1H} NMR spectroscopies. Their structures in solid state were determined by X-ray diffraction analyses, which accord with their spectroscopic characteristics.

Modulation of S‐Centered Reactivity: Impact of Terminal Ligands on Alkynyl Addition in [Fe2(μ‐S2)(CO)4L2] Complexes

“…Heating the solution at 40 °C moderately accelerated the reaction time without decomposition into monometallic species, as previously reported for such 1,2-dithiolene bimetallic complexes. [34,43] The IR spectrum of 7 Ph shows, in the ν CO region, a typical pattern for monosubstituted derivatives [Fe 2 (μ-dithiolate)(CO) 5 (L)], with four strong bands at 2051, 1993, 1980 (sh) and 1936 cm À 1 (Figure S6). The 1 H NMR spectrum in CD 2 Cl 2 is consistent with the formula [Fe 2 (μ-SCH=C(Ph)S)(CO) 5 L], with a singlet resonance of SCH= observed at 5.69 ppm.…”