An intermediate cobalt(IV) nitrido complex and its N-migratory insertion product.

Zolnhofer E, Käß M, Khusniyarov M, Heinemann FW, Maron L, Van Gastel M, Bill E, Meyer K (2014)

Publication Status: Published

Publication Type: Journal article

Publication year: 2014

Journal

Book Volume: 136

Pages Range: 15072-8

Journal Issue: 42

DOI: 10.1021/ja508144j

Abstract

Low-temperature photolysis experiments (T = 10 K) on the tripodal azido complex [(BIMPN(Mes,Ad,Me))Co(II)(N3)] (1) were monitored by EPR spectroscopy and support the formation of an exceedingly reactive, high-valent Co nitrido species [(BIMPN(Mes,Ad,Me))Co(IV)(N)] (2). Density functional theory calculations suggest a low-spin d(5), S = 1/2, electronic configuration of the central cobalt ion in 2 and, thus, are in line with the formulation of complex 2 as a genuine, low-spin Co(IV) nitride species. Although the reactivity of this species precludes handling above 50 K or isolation in the solid state, the N-migratory insertion product [(NH-BIMPN(Mes,Ad,Me))Co(II)](BPh4) (3) is isolable and was reproducibly synthesized as well as fully characterized, including CHN elemental analysis, paramagnetic (1)H NMR, IR, UV-vis, and EPR spectroscopy as well as SQUID magnetization and single-crystal X-ray crystallography studies. A computational analysis of the reaction pathway 2 → 3 indicates that the reaction readily occurs via N-migratory insertion into the Co-C bond (activation barrier of 2.2 kcal mol(-1)). In addition to the unusual reactivity of the nitride 2, the resulting divalent cobalt complex 3 is a rare example of a trigonal pyramidal complex with four different donor ligands of a tetradentate chelate-an N-heterocyclic carbene, a phenolate, an imine, and an amine-binding to a high-spin Co(II) ion. This renders complex 3 chiral-at-metal.

Authors with CRIS profile

Involved external institutions

Université Fédérale de Toulouse Midi-Pyrénées France (FR) Max-Planck-Institut für Chemische Energiekonversion (MPI CEC) / Max-Planck-Institute for Chemical Energy Conversion Germany (DE)

How to cite

APA:

Zolnhofer, E., Käß, M., Khusniyarov, M., Heinemann, F.W., Maron, L., Van Gastel, M.,... Meyer, K. (2014). An intermediate cobalt(IV) nitrido complex and its N-migratory insertion product. Journal of the American Chemical Society, 136(42), 15072-8. https://dx.doi.org/10.1021/ja508144j

MLA:

Zolnhofer, Eva, et al. "An intermediate cobalt(IV) nitrido complex and its N-migratory insertion product." Journal of the American Chemical Society 136.42 (2014): 15072-8.

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