High-yield synthesis of heavy rare earth(<scp>iii</scp>) anhydrous solvates: known, new, and unexpected products
Ten anhydrous rare-earth (RE) chloride solvates were prepared by dehydration of RECl<sub>3</sub>·6H<sub>2</sub>O with triethylorthoformate (teof) in <i>O</i>-donor solvents as an accessible and general synthetic route. Reactions are quick, safe, mild, easily reproducible, and cost-effective. They run at room temperature or under reflux to give high-yield, pure crystalline products that are either new, such as [Gd<sub>2</sub>Cl<sub>4</sub>(μ-Cl)<sub>2</sub>(Pr<sup>i</sup>OH)<sub>6</sub>] (1) and [{GdCl(μ-Cl)<sub>2</sub>(thf)<sub>2</sub>}<sub>∞</sub>] (2), or obtained for the first time from teof, such as [GdCl<sub>3</sub>(thf)<sub>4</sub>] (3), <i>trans</i>-[MCl<sub>2</sub>(thf)<sub>5</sub>]<i>trans</i>-[MCl<sub>4</sub>(thf)<sub>2</sub>], M = Gd (4), Dy (6), and Y (7), [YbCl<sub>3</sub>(thf)<sub>3</sub>] (8), and [MCl<sub>3</sub>(dme)<sub>2</sub>], M = Gd (5), Dy (9), and Er (10). Structural and spectroscopic characterization is presented for all products, and variable-temperature magnetic susceptibility data are discussed for the Dy<sup>3+</sup> complexes 6 and 9. The latter behaves as a field-induced single-ion magnet for which theoretical (<i>ab initio</i>) and experimental data allowed a non-trivial assignment of overlapping high- (Orbach, <i>U</i><sub>eff</sub> 139 cm<sup>-1</sup>) and low-temperature (Raman, <i>w</i><sub>eff</sub> 46.8(2) cm<sup>-1</sup>) magnetic relaxation mechanisms (1 kOe field). Besides the main products, unanticipated Lewis and redox reactivity led to serendipitous 11, [({Gd<sub>3</sub>Cl<sub>4</sub>(μ-Cl)<sub>4</sub>(μ-H<sub>3</sub>CCOO)(C<sub>3</sub>H<sub>8</sub>O<sub>2</sub>)(Pr<sup>i</sup>OH)<sub>4</sub>}·Pr<sup>i</sup>OH)<sub>∞</sub>], and 12, [{(thf)<sub>2</sub>Cl<sub>2</sub>Gd(μ-Cl)<sub>2</sub>(μ<sub>3</sub>-O<sub>2</sub>)Gd(thf)<sub>3</sub>}<sub>2</sub>]·3thf, whose formation is discussed. The final RE<sup>3+</sup> anhydrous complexes serve as valuable starting materials for numerous substitution reactions in coordination and organometallic chemistry.
Authors
- Jaı́sa F. Soares (ORCID: https://orcid.org/0000-0002-2775-131X)
- Guilherme A. Barbosa
- Matteo Briganti (ORCID: https://orcid.org/0000-0001-8576-3792)
- Ronny R. Ribeiro (ORCID: https://orcid.org/0000-0002-5752-2673)
- Andersson Barison (ORCID: https://orcid.org/0000-0001-9381-8239)
- Giovana G. Nunes (ORCID: https://orcid.org/0000-0001-7052-2523)
- Francielli S. Santana (ORCID: https://orcid.org/0000-0003-4570-3044)
- David L. Hughes (ORCID: https://orcid.org/0000-0003-0621-204X)
- Giordano Poneti (ORCID: https://orcid.org/0000-0002-1712-4611)
- José Severiano Carneiro Neto (ORCID: https://orcid.org/0000-0001-6741-1590)
- Fabiano Yokaichiya (ORCID: https://orcid.org/0000-0002-6860-9053)
- Daniel Costa (ORCID: https://orcid.org/0000-0001-7549-8104)
- Leandro Piovan (ORCID: https://orcid.org/0000-0002-2835-5001)
- Bruno J. Stoeberl (ORCID: https://orcid.org/0000-0002-6930-4382)
- Sarita Wisbeck (ORCID: https://orcid.org/0000-0002-2832-6809)
- Siddhartha O. K. Giese (ORCID: https://orcid.org/0000-0002-2525-0220)
Institutions
- University of East Anglia (GB)
- Università degli Studi della Tuscia (IT)
- University of Florence (IT)
- Universidade Federal do Paraná (BR)
Publication Details
- Journal
- Dalton Transactions
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5dt00254k
- Primary Topic
- Lanthanide and Transition Metal Complexes
- Type
- article
- Field-Weighted Citation Impact
- 0.00