The coordination chemistry of a series of redox non-innocent N-tert-butyl-N-2-pyridyl (2-(tBuNO)py) nitroxides towards Ln(III) ions was explored. Reaction of Ln(N(SiMe3)2)3 (Ln = La, Ce, Pr, and Tb) with 3 equiv 2-(tBuNOH)py formed dimeric [Ln(2-(tBuNO)py)3]2 complexes. These dimers were all isostructural in the solid state. The [Ce(2-(tBuNO)py)3]2 dimer was oxidized to the monometallic Ce(2-(tBuNO)py)4 complex using 3 equiv of the neutral 2-(tBuNO)py radical. The cyclic voltammagram of Ce(2-(tBuNO)py)4 exhibited a metal based redox feature centered at �2.0 V versus an external ferrocene reference, indicating a significant stabilization of the +4 oxidation state of Ce by the 2-(tBuNO)py framework. The Ce(X-2-(tBuNO)py)4 (X = 5-Me, and 4-N(CH3)2) analogs were also synthesized to correlate the electron donating ability of the substituent on the pyridyl ring to the shift in CeIII/IV redox potential.

Coordination chemistry of N-tert-butyl-N-2-pyridyl nitroxides towards lanthanide(III) ions

244th National Meeting (2012)

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