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Singlet–Triplet Gaps of Cobalt Nitrosyls: Insights from Tropocoronand Complexes

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journal contribution
posted on 03.08.2015 by Kathrin H. Hopmann, Jeanet Conradie, Espen Tangen, Zachary J. Tonzetich, Stephen J. Lippard, Abhik Ghosh
A density functional theory (DFT) study of {CoNO}8 cobalt nitrosyl complexes containing the [n,n]­tropocoronand ligand (TC-n,n) has revealed a sharp reduction of singlet–triplet gaps as the structures change from near-square-pyramidal (for n = 3) to trigonal-bipyramidal with an equatorial NO (for n = 5, 6). An experimental reinvestigation of [Co­(TC-3,3)­(NO)] has confirmed that it is not paramagnetic, as originally reported, but diamagnetic, like all other {CoNO}8 complexes. Furthermore, DFT calculations indicate a substantial singlet–triplet gap of about half an eV or higher for this complex. At the other end of the series, low-energy, thermally accessible triplet states are predicted for [Co­(TC-6,6)­(NO)]. Enhanced triplet-state reactivity may well provide a partial explanation for the failure to isolate this compound as a stable species.