Abstract
The iron(II) complex 1 of a macrocyclic tetracarbene binds NO to form a low-spin (S = (1)/2) {FeNO}(7) complex (2) with a linear FeNO unit and a short Fe-NO bond. IR, electron paramagnetic resonance, and Mössbauer spectroscopies as well as density functional theory calculations suggest some Fe(I)NO(+) character and reveal that the singly occupied molecular orbital of 2, resulting from the σ-antibonding interaction of Fe dz(2) and the NO lone pair, is largely iron-based. Reduction yields a quite stable {FeNO}(8) species (3); both 2 and 3 feature very low Mössbauer isomer shifts (∼0.0 mm·s(-1)).
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