On the usability of salt metathesis reactions for the synthesis of sterically crowded tris-formamidinate Ln(III) complexes: success and limits. Spontaneous reduction of Eu(III) to Eu(II)

On the usability of salt metathesis reactions for the synthesis of sterically crowded tris-formamidinate Ln(III) complexes: success and limits. Spontaneous reduction of Eu(III) to Eu(II) Full article

Journal

New Journal of Chemistry
ISSN: 1369-9261 , E-ISSN: 1144-0546

Output data

Year: 2022, Volume: 46, Number: 25, Pages: 11994-12001 Pages count : 8 DOI: 10.1039/D2NJ01589G

Authors

Bashirov Denis A. ¹ , Kolybalov Dmitry S. ² , Mironova Olga A. ¹ , Sukhikh Taisiya S. ¹ , Konchenko Sergey N. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry SB RAS
2	Department of Natural Sciences, Novosibirsk State University

The homoleptic [Ln(FormDipp)3] (FormDipp– = CH(NDipp)2 – (Dipp = 2,6-diisopropylphenyl), Ln = Nd, Eu) complexes bearing three bulky formamidinate ligands were successfully obtained using the salt metathesis approach, viz. the reaction of [Ln(FormDipp)2Cl(thf)n] (Ln = Nd (n = 2), Ln = Eu (n = 1)) with K(FormDipp) in toluene at 100 ?C. This method is not useful for the Ln smaller than Eu: all attempts to realize it for Gd and Tb were unsuccessful. In the case of Eu, the tris-formamidinate complex was obtained in toluene, but in a thf/toluene mixture, a spontaneous reduction of Eu(III) to Eu(II) leading to the formation of [Eu(FormDipp)2(thf)2] was observed. The Eu(III) to Eu(II) conversion is rather sterically induced. UV-Vis spectroscopy monitoring of the reaction indicates it to be a zero-order process. Possible routes of the reaction are proposed.

Bashirov D.A. , Kolybalov D.S. , Mironova O.A. , Sukhikh T.S. , Konchenko S.N.
On the usability of salt metathesis reactions for the synthesis of sterically crowded tris-formamidinate Ln(III) complexes: success and limits. Spontaneous reduction of Eu(III) to Eu(II)
New Journal of Chemistry. 2022. V.46. N25. P.11994-12001. DOI: 10.1039/D2NJ01589G WOS Scopus РИНЦ OpenAlex

Web of science:	WOS:000806452600001
Scopus:	2-s2.0-85131968280
Elibrary:	48724467
OpenAlex:	W4293193070

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