Ligand exchange and spin state equilibria of Fe II(N4Py) and related complexes in aqueous media

Apparao Draksharapu, Qian Li, Hella Logtenberg, Tieme A. Van Den Berg, Auke Meetsma, J. Scott Killeen, Ben L. Feringa, Ronald Hage, Gerard Roelfes, Wesley R. Browne

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We report the characterization and solution chemistry of a series of Fe II complexes based on the pentadentate ligands N4Py (1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine), MeN4Py (1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)ethanamine), and the tetradentate ligand Bn-N3Py (N-benzyl-1,1-di(pyridin-2-yl)-N-(pyridin-2- ylmethyl)methanamine) ligands, i.e., [Fe(N4Py)(CH 3CN)](ClO 4) 2 (1), [Fe(MeN4Py)(CH 3CN)](ClO 4) 2 (2), and [Fe(Bn-N3Py)(CH 3CN) 2](ClO 4) 2 (3), respectively. Complexes 2 and 3 are characterized by X-ray crystallography, which indicates that they are low-spin Fe II complexes in the solid state. The solution properties of 1-3 are investigated using 1H NMR, UV/vis absorption, and resonance Raman spectroscopies, cyclic voltammetry, and ESI-MS. These data confirm that in acetonitrile the complexes retain their solid-state structure, but in water immediate ligand exchange of the CH 3CN ligand(s) for hydroxide or aqua ligands occurs with full dissociation of the polypyridyl ligand at low (<3) and high (>9) pH. pH jumping experiments confirm that over at least several minutes the ligand dissociation observed is fully reversible for complexes 1 and 2. In the pH range between 5 and 8, complexes 1 and 2 show an equilibrium between two different species. Furthermore, the aquated complexes show a spin equilibrium between low- and high-spin states with the equilibrium favoring the high-spin state for 1 but favoring the low-spin state for 2. Complex 3 forms only one species over the pH range 4-8, outside of which ligand dissociation occurs. The speciation analysis and the observation of an equilibrium between spin states in aqueous solution is proposed to be the origin of the effectiveness of complex 1 in cleaving DNA in water with 3O 2 as terminal oxidant.

Original languageEnglish (US)
Pages (from-to)900-913
Number of pages14
JournalInorganic chemistry
Issue number2
StatePublished - Jan 16 2012


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