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Issue 31, 2018
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Heteroleptic samarium(iii) halide complexes probed by fluorescence-detected L3-edge X-ray absorption spectroscopy

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Abstract

The addition of various oxidants to the near-linear Sm(II) complex [Sm(N††)2] (1), where N†† is the bulky bis(triisopropylsilyl)amide ligand {N(SiiPr3)2}, afforded a family of heteroleptic three-coordinate Sm(III) halide complexes, [Sm(N††)2(X)] (X = F, 2-F; Cl, 2-Cl; Br, 2-Br; I, 2-I). In addition, the trinuclear cluster [{Sm(N††)}32-I)33-I)2] (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(SiMe3)2} (N′′). Complexes 2-X and 3 have been characterised by single crystal X-ray diffraction, elemental analysis, multinuclear NMR, FTIR and electronic spectroscopy. The Lα1 fluorescence-detected X-ray absorption spectra recorded at the Sm L3-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.

Graphical abstract: Heteroleptic samarium(iii) halide complexes probed by fluorescence-detected L3-edge X-ray absorption spectroscopy

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Supplementary files

Article information


Submitted
12 Apr 2018
Accepted
03 May 2018
First published
04 May 2018

This article is Open Access

Dalton Trans., 2018,47, 10613-10625
Article type
Paper

Heteroleptic samarium(III) halide complexes probed by fluorescence-detected L3-edge X-ray absorption spectroscopy

C. A. P. Goodwin, B. L. L. Réant, J. G. C. Kragskow, I. M. DiMucci, K. M. Lancaster, D. P. Mills and S. Sproules, Dalton Trans., 2018, 47, 10613
DOI: 10.1039/C8DT01452C

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