Hydride Reactivity of NiII[BOND]X[BOND]NiII Entities: Mixed-Valent Hydrido Complexes and Reversible Metal Reduction

Gehring H, Metzinger R, Herwig C, Intemann J, Harder S, Limberg C (2013)

Publication Status: Accepted

Publication Type: Journal article, Original article

Publication year: 2013

Journal

Chemistry - A European Journal Wiley-VCH Verlag

Original Authors: Gehring, H., Metzinger, R., Herwig, C., Intemann, J., Harder, S., Limberg, C.

Publisher: Wiley-VCH Verlag

Book Volume: 19

Pages Range: 1629 - 1636

Journal Issue: 19

DOI: 10.1002/chem.201203201

Abstract

After the lithiation of PYR-H (PYR=[{NC(Me)C(H) C(Me)NCH(iPr)}(C HN)]), which is the precursor of an expanded β-diketiminato ligand system with two binding pockets, its reaction with [NiBr(dme)] led to a dinuclear nickel(II)-bromide complex, [(PYR)Ni(μ-Br)NiBr] (1). The bridging bromide ligand could be selectively exchanged for a thiolate ligand to yield [(PYR)Ni(μ-SEt)NiBr] (3). In an attempt to introduce hydride ligands, both compounds were treated with KHBEt. This treatment afforded [(PYR)Ni(μ-H)Ni] (2), which is a mixed valent Ni-μ-H-Ni complex, and [(PYR-H)Ni(μ-SEt)Ni] (4), in which two tricoordinated Ni moieties are strongly antiferromagnetically coupled. Compound 4 is the product of an initial salt metathesis, followed by an intramolecular redox process that separates the original hydride ligand into two electrons, which reduce the metal centres, and a proton, which is trapped by one of the binding pockets, thereby converting it into an olefin ligand on one of the Ni centres. The addition of a mild acid to complex 4 leads to the elimination of H and the formation of a NiNi compound, [(PYR)Ni(μ-SEt)NiOTf] (5), so that the original Ni(μ-SEt) NiX core of compound 3 is restored. All of these compounds were fully characterized, including by X-ray diffraction, and their molecular structures, as well as their formation processes, are discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Authors with CRIS profile

Sjoerd Harder Lehrstuhl für Anorganische und Metallorganische Chemie

Involved external institutions

Humboldt-Universität zu Berlin DE Germany (DE) University of Groningen / Rijksuniversiteit Groningen NL Netherlands (NL)

How to cite

APA:

Gehring, H., Metzinger, R., Herwig, C., Intemann, J., Harder, S., & Limberg, C. (2013). Hydride Reactivity of NiII[BOND]X[BOND]NiII Entities: Mixed-Valent Hydrido Complexes and Reversible Metal Reduction. Chemistry - A European Journal, 19(19), 1629 - 1636. https://doi.org/10.1002/chem.201203201

MLA:

Gehring, Henrike, et al. "Hydride Reactivity of NiII[BOND]X[BOND]NiII Entities: Mixed-Valent Hydrido Complexes and Reversible Metal Reduction." Chemistry - A European Journal 19.19 (2013): 1629 - 1636.

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