Torres Ruiz, AlejandroVicent, D.J.Collado, A.Gómez Gallego, María Del MarDe Arellano, C.R.Sierra, M.A.2024-09-052024-09-052023Organometallics 2023, 42, 4, 316–3261520-60411520-60410276-733310.1021/acs.organomet.2c00549https://hdl.handle.net/20.500.14352/107945A new phosphite ligand having three [(μ-ADT)RFe2(CO)6] (R= p-HOC6H4) moieties (2) has been prepared in good yield by the reaction of complex [(μ-ADT)RFe2(CO)6] (R= p-HOC6H4) 1a with PCl3. Coordination of this phosphite to [PdCl2(MeCN)2] or [PtCl2(DMSO)2] forms heterometallic square planar complexes 5 (C84H48Cl2Fe12N6O42P2MS12) (M = Pt, Pd) in excellent yields. Three-legged piano stool complexes 6 (C52H39Cl2Fe6N3O21PMS6) (M = Rh, Ir) were obtained by the reaction of phosphite 2 with [MCl2Cp*]2 (M = Rh, Ir) in good yields. The formation of complexes 5 and 6 demonstrates the versatility of this new ligand for forming different heteropolymetallic complexes under mild reaction conditions. Moreover, the open-chain derivatives [(μ-ADT)RFe2(CO)6] (R= HOCH2CH2, o-HOC6H4) (1b and 1c, respectively) form cyclic complexes 4 by spontaneous intramolecular CO substitution by the P atom in one of the three [FeFe] fragments. The electrocatalytic behavior of complexes 2 and 4 upon the addition of AcOH is similar to that of related [(μ-ADT)Fe2(CO)6] derivatives. The successive additions of AcOH cause an increase in the current intensity in the wave at about −1.80 V for heteropolymetallic complexes 5 and 6. However, the appearance of a new wave around −1.40 V in complexes 5 points to an acid-promoted side reaction in the electrochemical process.engAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/journal article1520-6041https://pubs.acs.org/doi/10.1021/acs.organomet.2c00549open access547Química orgánica (Química)2306 Química Orgánica