Water-soluble Co3C and Co2C2 clusters; redox chemistry and electrochemical reactions in water

Abstract

The water-soluble clusters [Co₃(CR)(CO)₈L]^n–{n= 1 or 3, L =[PPh_3–n(C₆H₄SO₃-m)_n]^n–; R = Ph, Me, Cl or Br} and [Co₂{C₂(CO₂Me)₂}(CO)₅{P(C₆H₄SO₃-m)₃}]^3–(two isomers) have been prepared and characterised. Attempts were also made to sulfonate the capping aryl group of [Co₃(CPh)(CO)₉]. The redox processes of these complexes in water, ‘wet’ and ‘dry’ solvents have been investigated; C and C mechanisms, similar to those elucidated for non-aqueous solvents, operate in water but the large sulfonated ligands influence the kinetic parameters. The need to use dry solvents for electrochemical studies of these clusters may not be as important as previously thought.