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Issue 6, 2009
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Cationic and neutral NiII complexes containing a non-innocent PNP ligand: formation of alkyl and thiolate species

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Abstract

The synthesis and characterization of a series of cationic and neutral Ni-complexes with the non-innocent PNPtBu pincer ligand is discussed. Starting with the dicationic complex 1, [Ni(PNPtBu)(NCMe)](BF4)2, a small series of dicationic and monocationic NiII complexes has been prepared. Substitution with tert-butyl isocyanide and azide occurs readily in MeCN solution. IR spectroscopy provided a practical handle to access the formal valence state of the ligand. For the mono- and dicationic tert-butyl isocyanide species 3 and 6 the main vibrational bands in the IR spectra were reproduced quantitatively by DFT theoretical calculations, showing good agreement with the experimentally observed Δν upon dearomatization of the PNPtBu backbone. Using a selective dearomatization-reprotonation methodology the mononuclear Ni-thiolate species 7 and 8 are cleanly generated and their structures have been determined by X-ray crystal structure determination. Alternatively, starting from the monocationic species [Ni(PNPtBu)Cl]BF4, neutral alkyl derivatives are easily available in a two-step procedure, and these species have been spectroscopically characterized.

Graphical abstract: Cationic and neutral NiII complexes containing a non-innocent PNP ligand: formation of alkyl and thiolate species

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Publication details

The article was received on 26 Aug 2008, accepted on 04 Nov 2008 and first published on 16 Dec 2008


Article type: Paper
DOI: 10.1039/B814806F
Citation: Dalton Trans., 2009, 1016-1023
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    Cationic and neutral NiII complexes containing a non-innocent PNP ligand: formation of alkyl and thiolate species

    J. I. van der Vlugt, M. Lutz, E. A. Pidko, D. Vogt and A. L. Spek, Dalton Trans., 2009, 1016
    DOI: 10.1039/B814806F

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