Synthesis and reactivity of a β-diketiminate SmII complex†
Niels J. C. van Velzen A and Sjoerd Harder
B *
+ Author Affiliations
- Author Affiliations
A Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
B Inorganic and Organometallic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany.
Australian Journal of Chemistry 75(9) 549-557 https://doi.org/10.1071/CH21296
Submitted: 13 November 2021 Accepted: 13 December 2021 Published: 8 March 2022
© 2022 The Author(s) (or their employer(s)). Published by CSIRO Publishing.
Abstract
Attempts to stabilise a TmII metal centre with the bulky β-diketiminate ligand HC[C(Me)=N(DIPP)]2 (BDI) failed (DIPP, 2,6-diisopropylphenyl). Reaction of TmI2 and 2 equiv. (BDI)K gave the TmIII complex (BDI)(BDI-H)Tm (1) in which (BDI-H)2− is a doubly deprotonated ligand. However, following the same route, (BDI)2Sm (2) was isolated in 48% crystalline yield. Complex 2 is highly soluble in aromatic solvents or alkanes and was reacted with various reagents like phenazine, PhSSPh, O2, NO, cuminil and fluorenone. This led to isolation and structural characterisation of the following SmIII complexes: [(BDI)2Sm]2(μ-phenazine) (3), [(BDI)Sm(SPh)(μ-SPh)]2 (4), (BDI)(BDI-H)Sm (5a), (BDI)2Sm(OC13H8) (6) and (BDI)2Sm(NO2) (7). The rich redox reactivity of (BDI)2Sm (2) and its very high solubility in apolar solvents like hexane make it an attractive reducing agent in synthesis.
Keywords: β-diketiminate, chelating ligand, reactivity, redox chemistry, samarium, synthesis, thulium, X-ray diffraction.
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