Synthesis and Reactivity of a Cerium(III) Scorpionate Complex Containing a Redox Non-Innocent 2,2′-Bipyridine Ligand
School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK
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Academic Editors: Stephen Mansell and Steve Liddle
Inorganics 2015, 3(4), 534-553; https://doi.org/10.3390/inorganics3040534
Received: 14 September 2015 / Revised: 30 October 2015 / Accepted: 17 November 2015 / Published: 27 November 2015
(This article belongs to the Special Issue Rare Earth and Actinide Complexes)
The Ce(III) hydrotris(3,5-dimethylpyrazolyl)borate complex [Ce(TpMe2)2(κ2-dmpz)] (1) (TpMe2 = {HB(dmpz)3}−; dmpz = 3,5-dimethylpyrazolide) was isolated in fair yield from the reaction of [Ce(I)3(THF)4] with two equivalents of [K(TpMe2)] via the facile decomposition of TpMe2. [Ce(TpMe2)2(bipy)] (2) was synthesized in poor yield by the “one-pot” reaction of [Ce(I)3(THF)4], bipy (bipy = 2,2′-bipyridine), KC8 and two equivalents of [K(TpMe2)] in tetrahydrofuran (THF). The reaction of 2 with N-methylmorpholine-N-oxide produced the known decomposition product [Ce(TpMe2)(μ-BOpMe2)]2 (3) (BOpMe2 = {HBO(dmpz)2}2−) in poor yield, presumably by N–O and B–N bond cleavage of a reactive intermediate. The reaction of 2 with trimethylsilylazide gave [Ce(TpMe2)2(N3)] (4) in poor yield; the fate of bipy and the trimethylsilyl group is unknown. Complexes 1–4 were characterized by single crystal XRD, NMR and FTIR spectroscopy and elemental analysis. Complex 2 was additionally probed by UV/Vis/NIR and Electron Paramagnetic Resonance (EPR) spectroscopies, Cyclic Voltammetry (CV) and magnetometry, which together indicate a formal 4f1 Ce(III) center coordinated by a bipy·− radical anion in this system.
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Keywords:
lanthanide; cerium; scorpionate; tris(pyrazolyl)borate; radical; redox non-innocent
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MDPI and ACS Style
Ortu, F.; Zhu, H.; Boulon, M.-E.; Mills, D.P. Synthesis and Reactivity of a Cerium(III) Scorpionate Complex Containing a Redox Non-Innocent 2,2′-Bipyridine Ligand. Inorganics 2015, 3, 534-553.
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