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  Spin Isomers and Ligand Isomerization in a Three-Coordinate Cobalt(I) Carbonyl Complex

Al-Afyouni, M. H., Suturina, E., Pathak, S., Atanasov, M., Bill, E., DeRosha, D. E., et al. (2015). Spin Isomers and Ligand Isomerization in a Three-Coordinate Cobalt(I) Carbonyl Complex. Journal of the American Chemical Society, 137(33), 10689-10699. doi:10.1021/jacs.5b06078.

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 Creators:
Al-Afyouni, Malik H.1, Author
Suturina, Elizaveta2, 3, Author              
Pathak, Shubhrodeep2, Author              
Atanasov, Mihail2, 4, Author              
Bill, Eckhard2, Author              
DeRosha, Daniel E.5, Author
Brennessel, William W.1, Author
Neese, Frank2, Author              
Holland, Patrick L.1, 5, Author
Affiliations:
1Department of Chemistry, University of Rochester, Rochester, New York 14618, United States, ou_persistent22              
2Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
3Novosibirsk State University, Pirogova Street 2, 630090 Novosibirsk, Russia, ou_persistent22              
4Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Akademy Georgi Bontchev Street 11, 1113 Sofia, Bulgaria, ou_persistent22              
5Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States, ou_persistent22              

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 Abstract: Hemilabile ligands, which have one donor that can reversibly bind to a metal, are widely used in transition-metal catalysts to create open coordination sites. This change in coordination at the metal can also cause spin-state changes. Here, we explore a cobalt(I) system that is poised on the brink of hemilability and of a spin-state change and can rapidly interconvert between different spin states with different structures (“spin isomers”). The new cobalt(I) monocarbonyl complex LtBuCo(CO) (2) is a singlet (12) in the solid state, with an unprecedented diketiminate binding mode where one of the C═C double bonds of an aromatic ring completes a pseudo-square-planar coordination. Dissolving the compound gives a substantial population of the triplet (32), which has exceptionally large uniaxial zero-field splitting due to strong spin–orbit coupling with a low-lying excited state. The interconversion of the two spin isomers is rapid, even at low temperature, and temperature-dependent NMR and electronic absorption spectroscopy studies show the energy differences quantitatively. Spectroscopically validated computations corroborate the presence of a low minimum-energy crossing point (MECP) between the two potential energy surfaces and elucidate the detailed pathway through which the β-diketiminate ligand “slips” between bidentate and arene-bound forms: rather than dissociation, the cobalt slides along the aromatic system in a pathway that balances strain energy and cobalt–ligand bonding. These results show that multiple spin states are easily accessible in this hemilabile system and map the thermodynamics and mechanism of the transition.

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Language(s): eng - English
 Dates: 2015-06-112015-08-122015-08-26
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.5b06078
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 137 (33) Sequence Number: - Start / End Page: 10689 - 10699 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870