Heteroleptic samarium(iii) halide complexes probed by fluorescence-detected L-edge X-ray absorption spectroscopy.

Author(s) Goodwin, C.A.P.; Réant, B.L.L.; Kragskow, J.G.C.; DiMucci, I.M.; Lancaster, K.M.; Mills, D.P.; Sproules, S.
Journal Dalton Trans
Date Published 2018 Aug 21
Abstract

The addition of various oxidants to the near-linear Sm(ii) complex [Sm(N)] (1), where N is the bulky bis(triisopropylsilyl)amide ligand {N(SiPr)}, afforded a family of heteroleptic three-coordinate Sm(iii) halide complexes, [Sm(N)(X)] (X = F, 2-F; Cl, 2-Cl; Br, 2-Br; I, 2-I). In addition, the trinuclear cluster [{Sm(N)}(μ-I)(μ-I)] (3), which formally contains one Sm(ii) and two Sm(iii) centres, was isolated during the synthesis of 2-I. Complexes 2-X are remarkably stable towards ligand redistribution, which is often a facile process for heteroleptic complexes of smaller monodentate ligands in lanthanide chemistry, including the related bis(trimethylsilyl)amide {N(SiMe)} (N''). Complexes 2-X and 3 have been characterised by single crystal X-ray diffraction, elemental analysis, multinuclear NMR, FTIR and electronic spectroscopy. The Lα fluorescence-detected X-ray absorption spectra recorded at the Sm L-edge for 2-X exhibited a resolved pre-edge peak defined as an envelope of quadrupole-allowed 2p → 4f transitions. The X-ray absorption spectral features were successfully reproduced using time-dependent density functional theoretical (TD-DFT) calculations that synergistically support the experimental observations as well as the theoretical model upon which the electronic structure and bonding in these lanthanide complexes is derived.

DOI 10.1039/c8dt01452c
ISSN 1477-9234
Citation Goodwin CA, Réant BL, Kragskow JG, DiMucci IM, Lancaster KM, Mills DP, et al. Heteroleptic samarium(iii) halide complexes probed by fluorescence-detected L-edge X-ray absorption spectroscopy. Dalton Trans. 2018;47(31):10613-10625.

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