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| ID:
708962.0,
MPI für bioanorganische Chemie / MPI für bioanorganische Chemie |
| An Intermediate Cobalt(IV) Nitrido Complex and its N-Migratory Insertion Product. |
| Authors: | Zolnhofer, Eva M.; Käss, Martina; Khusniyarov, Marat M.; Heinemann, Frank W.; Maron, Laurent; van Gastel, Maurice; Bill, Eckhard; Meyer, Karsten | | Language: | English | | Date of Publication (YYYY-MM-DD): | 2014 | | Title of Journal: | Journal of the American Chemical Society | | Journal Abbrev.: | J. Am. Chem. Soc. | | Volume: | 136 | | Issue / Number: | 42 | | Start Page: | 15072 | | End Page: | 15078 | | Review Status: | Internal review | | Audience: | Experts Only | | Abstract / Description: | Low-temperature photolysis experiments (T = 10 K) on the tripodal azido complex [(BIMPNMes,Ad,Me)Co-II(N-3)] (1) were monitored by EPR spectroscopy and support the formation of an exceedingly reactive, high-valent Co nitrido species [(BIMPNMes,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-BIMPNMes,Ad,Me)Co-II](BPh4) (3) is isolable and was reproducibly synthesized as well as fully characterized, including CHN elemental analysis, paramagnetic H-1 NMR, IR, UVvis, 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 CoC 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 chelatean N-heterocyclic carbene, a phenolate, an imine, and an aminebinding to a high-spin Co(II) ion. This renders complex 3 chiral-at-metal. | | External Publication Status: | published | | Document Type: | Article |
| Communicated by: | N. N. | | Affiliations: | MPI für bioanorganische Chemie
| | External Affiliations: | [Zolnhofer,E.M.; Käss,M.; Khusniyarov,M.M.; Heinemann,F.W.; Meyer,K.;]Univ.Erlangen Nürnberg, Dept.Chem.& Pharm., D-91058 Erlangen, Germany.
[Maron,L.;] Univ.Toulouse, F-31077 Toulouse, France.
| | Identifiers: | ISI:000343686500065 [ID No:1]
ISSN:0002-7863 [ID No:2]
DOI:10.1021/ja508144j [ID No:3] | |
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