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RESEARCH ARTICLE
Contents Vol 75(9)

Reduction of phosphine sulfides and selenides by samarium(ii) formamidinate as an approach to binuclear mono- and dichalcogenide complexes†

Boris Yu. Savkov A , Taisiya S. Sukhikh A , Sergey N. Konchenko A * and Nikolay A. Pushkarevsky https://orcid.org/0000-0001-8668-6362 A *
+ Author Affiliations
- Author Affiliations

A Nikolaev Institute of Inorganic Chemistry SB RAS, Akademika Lavrentieva Avenue 3, 630090 Novosibirsk, Russia.

* Correspondence to: konch@niic.nsc.ru, nikolay@niic.nsc.ru

Handling Editor: George Koutsantonis

Australian Journal of Chemistry 75(9) 732-745 https://doi.org/10.1071/CH21271
Submitted: 19 October 2021  Accepted: 17 February 2022   Published: 16 August 2022

© 2022 The Author(s) (or their employer(s)). Published by CSIRO Publishing.

Abstract

The reductive action of the bulky SmII formamidinate complex [Sm(dippForm)2(thf)2] (dippForm− = HC(Ndipp)2−, dipp = 2,6-diisopropylphenyl; thf = tetrahydrofuran) (1) on a series of phosphine chalcogenides (R3PE = Ph3PO, Ph3PS, Ph3PSe, nBu3PS, nBu3PSe) as well as Ph3AsS, has been investigated. The reactions are fast for the phosphine derivatives with E = Se and for Ph3AsS, and slow for the phosphine sulfides. They lead to mixtures of binuclear mono- and dichalcogenide complexes [(Sm(dippForm)2)2(µ-En)] (E = S (2), Se (3); n = 1, 2). The ratio of species with (µ-E) or (µ-η2:η2-E2) bridges depends on the nature of the chalcogenide reactant and its concentration, but even under its local excess the formation of the monochalcogenide is preferential. Both types of species form isostructural solid solutions. The dense outer packing of dippForm ligands in the complexes 2 and 3, leaving enough free space in the centre of the molecule, is thought to be the main reason for the geometrical similarity of mono- and dichalcogenides and for their ready co-crystallization. A reaction scheme is proposed, involving the coordination of the starting chalcogenide to the SmII centre with successive formation of E-centered transient radical species [Sm(dippForm)2(E˙)]. Contrary to the phosphine/arsine sulfides and selenides, the product of phosphine oxide coordination, [Sm(dippForm)2(OPPh3)] (4), was shown to be stable, while a similar complex with two phosphine oxide ligands, [Sm(dippForm)2(OPPh3)2] (5), was fortuitously crystallized at lower temperatures.

Keywords: arsine sulphide, chalcogenide, formamidinate, lanthanide, molecular structure, radical intermediate, reaction pathway, reductive reactivity.


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