1136166-96-5Relevant academic research and scientific papers
Cationic and neutral NiII complexes containing a non-innocent PNP ligand: Formation of alkyl and thiolate species
Van Der Vlugt, Jarl Ivar,Lutz, Martin,Pidko, Evgeny A.,Vogt, Dieter,Spek, Anthony L.
, p. 1016 - 1023 (2009)
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)](BF 4)2, a small series of dicationic and monocationic Ni II 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. The Royal Society of Chemistry 2009.
