RT Journal Article
T1 Heteropolymetallic [FeFe]-hydrogenase mimics: synthesis and electrochemical properties
A1 Torres Ruiz, Alejandro
A1 Collado Martínez, Alba
A1 Gómez Gallego, María Del Mar
A1 Ramírez de Arellano, Carmen
A1 Sierra Rodríguez, Miguel Ángel
AB The synthesis and electrochemical properties of tetranuclear[Fe2S2]-hydrogenase mimic species containing Pt(II), Ni(II), and Ru(II)complexes have been studied. To this end, a new tetranuclear [Fe2S2] complexcontaining a 5,5′- diisocyanide-2,2′-bipyridine bridging ligand has been designedand coordinated to the metal complexes through the bipyridine moiety. Thus, thetetranuclear [Fe2S2] complex (6) coordinates to Pt(II), Ni(II) and Ru(II) yieldingthe corresponding metal complexes. The new metal center in the bipyridine linkermodulates the electronic communication between the redox-active [Fe2S2] units. Thus, electrochemical studies and DFT calculations have shown that the presenceof metal complexes in the structure strongly affect the electronic communicationbetween the [Fe2S2] centers. In the case of diphosphine platinum compounds 10,the structure of the phosphine ligand plays a crucial role to facilitate or to hinderthe electronic communication between [Fe2S2] moieties. Compound 10a, bearing a dppe ligand, shows weak electroniccommunication (ΔE = 170 mV), whereas the interaction is much weaker in the Pt-dppp derivative 10b (ΔE = 80 mV) and virtuallynegligible in the Pt-dppf complex 10c. The electronic communication is facilitated by incorporation of a Ru-bis(bipyridine) complex,as observed in the BF4 salt 12 (ΔE = 210 mV) although the reduction of the [FeFe] centers occurs at more negative potentials. Overall, the experimental−computational procedure used in this work allows us to study the electronic interaction between theredox-active centers, which, in turn, can be modulated by a transition metal.
PB ACS
SN 0020-1669
YR 2023
FD 2023
LK https://hdl.handle.net/20.500.14352/108015
UL https://hdl.handle.net/20.500.14352/108015
LA eng
NO Inorganic Chemistry  2023, 62, 8, 3409-3419
DS Docta Complutense
RD 8 jun 2025