Singlet–Triplet Gaps of Cobalt Nitrosyls: Insights from Tropocoronand Complexes
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Author(s)
Hopmann, Kathrin H.
Conradie, Jeanet
Tangen, Espen
Tonzetich, Zachary John
Lippard, Stephen J.
Ghosh, Abhik
Date Issued
July 2015
Journal
Inorganic Chemistry
Publisher
American Chemical Society (ACS)
Citation
Hopmann, Kathrin H., Jeanet Conradie, Espen Tangen, Zachary J. Tonzetich, Stephen J. Lippard, and Abhik Ghosh. “Singlet–Triplet Gaps of Cobalt Nitrosyls: Insights from Tropocoronand Complexes.” Inorg. Chem. 54, no. 15 (August 3, 2015): 7362–7367.
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Original manuscript
Abstract
A density functional theory (DFT) study of {CoNO}[superscript 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}[superscript 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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
http://dx.doi.org/10.1021/acs.inorgchem.5b00901
