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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†

Jarl Ivar van der Vlugt,‡*a   Martin Lutz,b   Evgeny A. Pidko,a   Dieter Vogta  and  Anthony L. Spekb  
Author affiliations

* Corresponding authors

a Schuit Institute of Catalysis, Laboratory of Homogeneous Catalysis, Department of Chemistry and Chemical Engineering, Eindhoven University of Technology, PO Box 513, Eindhoven, MB, the Netherlands
E-mail: j.i.v.d.vlugt@tue.nl
Fax: ++31 40 2455054
Tel: ++31 40 2475028

b Department of Crystal and Structural Chemistry, Utrecht University, Padualaan 8, CH Utrecht, the Netherlands

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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Article information

https://doi.org/10.1039/B814806F
Submitted
26 Aug 2008
Accepted
04 Nov 2008
First published
16 Dec 2008
Dalton Trans., 2009, 1016-1023
Article type
Paper
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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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