Intramolecular hydrogen bonding interaction, a mechanism for the bridging linkages to exert electronic influence on diiron models of [FeFe]-hydrogenase

Diiron hexacarbonyl complexes bearing naphthalene-1,8-dithiolate bridge moiety as mimics of the sub-unit of [FeFe]-hydrogenase: synthesis, characterisation and electrochemical investigations

“…Recently, we used DFT calculations to examine how a bridging linkage affects the compositions of the HOMOs and LUMOs of diiron hexacarbonyl mimics. 51 It was found that the linkage has significant influence on the compositions of the HOMOs, and the LUMOs were mainly located on the diiron centre in all the examples examined. However, the calculations (Table 5 and Fig.…”

“…Such an interaction is in agreement with what we found recently that intramolecular interaction exerts electronic influence on the frontier orbitals. 51 Among the complexes, complexes 3a and 3b show distinct features in their reductions from the other complexes. This is particularly obvious in DCM.…”

Synthesis, Characterization and Electrochemical Studies of bis(Monothiolato) {FeFe} Complexes [Fe2(μ‐SC6H4‐OMe‐m)2(CO)5L] (L = CO, PCy3, PPh3)

“…Only recently, the focus has shifted to monothiolate‐based {FeFe} systems. The limited examples reported include mostly hexacarbonyl and very few phosphine substituted mono‐ or diiron complexes [51–71] . Our group has also reported the redox and electrocatalytic properties of bis(monothiolato)‐based {FeFe} systems [72–77] wherein we have shown that the efficiency and stability of the catalysts vary with the type of monothiolate ligand used.…”