Heteroleptic Nickel Complexes of a Bulky Bis(carbene)borate Ligand [electronic resource]
Nickel Complexes; Nitrosyl Ligands, Nhc Complexes, Bidentate Ligands; Dioxygen Reactivity.
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| Online Access: |
Full Text (via OSTI) |
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| Format: | Government Document Electronic eBook |
| Language: | English |
| Published: |
Washington, D.C. : Oak Ridge, Tenn. :
United States. Department of Energy. Office of Basic Energy Sciences ; distributed by the Office of Scientific and Technical Information, U.S. Department of Energy,
2018.
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| Subjects: |
| Summary: | Nickel Complexes; Nitrosyl Ligands, Nhc Complexes, Bidentate Ligands; Dioxygen Reactivity. |
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| Abstract: | Bis(carbene)borate ligand transfer to the nickel nitrosyl synthon Ni(NO)(PPh<sub>3</sub>)<sub>2</sub>Br provides the new nickel nitrosyl complex Ph<sub>2</sub>B(<sup>t</sup>BuIm)<sub>2</sub>Ni(NO)(PPh<sub>3</sub>). The solid state structure reveals a trigonal pyramidal nickel ion with a very long bond to the apical PPh<sub>3</sub> ligand. The complex reversibly dissociates PPh<sub>3</sub> in solution to afford three-coordinate Ph<sub>2</sub>B(<sup>t</sup>BuIm)<sub>2</sub>Ni(NO), with NMR data providing evidence for PPh<sub>3</sub> binding at low temperatures. Ligand transfer to Ni(PMe<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub> provides the square planar complex, Ph<sub>2</sub>B(<sup>t</sup>BuIm)<sub>2</sub>Ni(PMe<sub>3</sub>)Cl, which shows no evidence for rearranging to the form a homoleptic complex with two bis(carbene)borate ligands. This complex is a suitable synthon for the [Ph<sub>2</sub>B(<sup>t</sup>BuIm)<sub>2</sub>Ni]<sup>+</sup> fragment, as demonstrated by the synthesis of the π-allyl complex Ph<sub>2</sub>B(<sup>t</sup>BuIm)<sub>2</sub>Ni(η<sup>3</sup>-C<sub>7</sub>H<sub>7</sub>). The π-allyl complex reacts with O<sub>2</sub> to provide benzaldehyde and an unstable complex that is tentatively identified as the nickel(II) hydroxide [Ph<sub>2</sub>B(<sup>t</sup>BuIm)<sub>2</sub>Ni(μ-OH)]<sub>2</sub> |
| Item Description: | Published through SciTech Connect. 09/25/2018. Polyhedron 156 1 ISSN 0277-5387 AM. Jorge L. Martinez; Wei-Tsung Lee; Maren Pink; Chun-Hsing Chen; Jeremy M. Smith. New Mexico State Univ., Las Cruces, NM (United States) |
| Physical Description: | p. 297-302 : digital, PDF file. |