Infrared spectroscopy, photoelectron spectroscopy, and electrochemistry of diasteromers of [(�-2,4-pentanedithiolato)][Fe(CO)3]2 have been studied.  Diastereomer 1  undergoes ring inversion of the six-membered dithiolato ring, but 2   does not to avoid 1,3-diaxial methyl interaction as demonstrated by variable temperature 1H NMR spectroscopy.  Infrared spectroscopy and photoelectron spectroscopy indicate that electronically 1  and 2  are nearly identical to [(�-1,3-propanedithiolato)][Fe(CO)3]2, 3  . However, reduction of 1  and 2  shows reversibility at all cyclic voltammetry scan rates, while 3  only approaches reversibility at faster scan rates.

Electronically similar and electrochemically dissimilar [(μ-2,4-pentanedithiolato)][Fe(CO)3]2 and [(μ-1,3-propanedithiolato)][Fe(CO)3]2: A structural, electrochemical, and computational study of diiron hydrogenase active site mimics

243rd National Meeting (2012)

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