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RESEARCH ARTICLE
Contents Vol 75(9)

Open samarocene and ytterbocenes and their adducts with N-heterocyclic carbene (NHC) and imidazolin-2-thiones†

Jan Raeder A , Jan H. Jördens A and Marc D. Walter https://orcid.org/0000-0002-4682-8749 A *
+ Author Affiliations
- Author Affiliations

A Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany.

* Correspondence to: mwalter@tu-bs-de

Handling Editor: George Koutsantonis

Australian Journal of Chemistry 75(9) 636-648 https://doi.org/10.1071/CH21326
Submitted: 6 December 2021  Accepted: 17 January 2022   Published: 9 March 2022

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

Abstract

Reaction of the open samarocene [(η5-pdl′)2Sm(thf)2] (1-Sm; pdl′ = 2,4-tBu2C5H5) towards IMes (= 1,3-dimesitylimidazolin-2-ylidene), ItBu (= 1,3-di-tert-butylimidazolin-2-ylidene) and IiPr2Me2 (= 1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene) forms the corresponding NHC adducts, [(pdl′)2Sm(IMes)] (2-Sm), [(pdl′)2Sm(ItBu)] (3-Sm) and [(pdl′)2Sm(IiPr2Me2)] (4-Sm), respectively in good to excellent yields. Diverging reactivity patterns emerge when we attempted to prepare the related adducts using the open ytterbocene [(pdl′)2Yb(thf)] (1-Yb). Attributed to the smaller ionic radius of YbII no adduct is observed for IMes. However, for the smaller ItBu ligand iso-butene elimination occurs to yield the imidazole YbII adduct (3′-Yb). For the slightly less sterically encumbered IiPr2Me2 two products were isolated, albeit in low yield: [(pdl′)2Yb(IiPr2Me2)] (4-Yb) and [{(pdl′)Yb(IiPr2Me2)(μ-S)}2] (5-Yb). The surprising formation of the μ-sulfido bridged species 5-Yb suggested that this product might result from trace impurities of imidazoline-2-thione originating from the synthesis of IiPr2Me2. To verify this hypothesis the first imidazoline-2-thione adducts in organolanthanide chemistry were prepared by the reaction of 1-Sm and 1-Yb towards S=IMe2Me2 and S=IiPr2Me2, respectively. All of these adducts were structurally authenticated. However, the imidazoline-2-thione adducts slowly degrade in solution with the Yb derivatives being less stable. Analyses of the organic degradation products suggest that reduction of imidazoline-2-thione to imidazoline-2-ylidene can indeed be accomplished by the lanthanide metal (providing one electron) as well as the (pdl′)− ligand (also delivering one electron).

Keywords: open metallocenes, N-heterocyclic carbenes, imidazolin-2-thiones, ytterbium, samarium.


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