The trend of incorporating redox-active ligands into metal complexes has become widespread over the past decade, and continues to expand. Redox-active ligands come in several varieties, the most notable being the quinone and metallocene families.We set out to explore redox-active ligands of the metallocene variety. These metalloligands feature clear distinctions of ligand oxidation state versus metal oxidation state, hence they can be deemed as redox-active, but innocent. Ligands were synthesized with redox couples cathodic of the ferrocene/ferrocenium couple (Fc0/+) by incorporating decamethylferrocene (Fc* = Fe(Cp*)2, Cp* = C5Me5) into a phosphine based ligand. The synthesis of two redox-active, innocent ligands is presented: FcP* (1 , FcP* = (Et2PCH2C5Me4)FeCp*) and FcP# (2 , FcP# = Et2PCH2C5Me4)FeCp#, Cp# = C5Me4H). In addition to hydrogenase enzyme modeling, these ligands have been incorporated into several other metal systems. The redox potentials of these metalloligands both attached and unattached to a metal center were analyzed. Figure 1. <img src='https://acs-archive-assets2.s3.amazonaws.com/239nm/uploads/10968_figure_1.jpg' alt='' />

Synthesis and applications of ferrocenyl phosphine ligands

246th National Meeting (2013)

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