Synthesis and Reactivity of an Iron–Tin Complex with Adjacent Stannylidyne and Ferriostannylene Units Article Swipe

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Yang Liu , Franz F. Westermair , Isabelle Becker , Sebastian Hauer , Michael Bodensteiner , Christoph Hennig , Gábor Balázs , Franc Meyer , Ruth M. Gschwind , Robert Wolf ·

YOU? · · 2025 · Open Access · · DOI: https://doi.org/10.1021/jacs.4c18423

Heavier transition metal carbyne analogs hold significant potential for cooperative activation of small molecules. However, complexes containing more than one heavier tetrylidyne ligand RE (E = Si, Ge, Sn, Pb) are rare due to the high oligomerization tendency of RE ligands. In this study, we describe the complex [Fe(SnAr')₂] (1; Ar' = 2,6-Dipp₂-C₆H₃, Dipp = 2,6-ⁱPr₂-C₆H₃), which features adjacent Fe-Sn single and double bonds. Complex 1 exhibits versatile reactivity with transition metal and main group compounds. Treatment of complex 1 with Ni(COD)₂ (COD = 1,5-cyclooctadiene) yields the tetranuclear complex [Fe(μ-SnAr')₂Ni] (2), characterized by an unusual "push-pull" interaction between nickel(0) and the two coordinating Sn atoms, as revealed by quantum chemical studies. The reaction of complex 1 with AlBr₃ results in Al-Br bond cleavage and Ar' migration to aluminum. CH₃I adds oxidatively to the Sn atom that is singly bonded to Fe, while PMe₃ coordinates to Fe, inducing reversible cleavage of the Fe═Sn double bond. In addition, complex 1 activates inorganic molecules. CO₂ undergoes disproportionation to produce a carbonate-bridged Ar'Sn(μ-OCO₂)SnAr' ligand, whereas CS₂ is reductively coupled to form an ethylene tetrathiolate ligand ([C₂S₄]^4-). The reaction with white phosphorus (P₄) generates an unusual Ar'P₄Sn₂Ar' ligand. This multifaceted reactivity illustrates the behavior of the Fe and Sn sites in complex 1, suggesting that complexes of this type are promising reagents for small molecule activation.

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Chemistry Tin Reactivity (psychology) Organic chemistry Alternative medicine Pathology Medicine

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Type: article
Language: en
Landing Page: https://doi.org/10.1021/jacs.4c18423
OA Status: hybrid
Cited By: 3
References: 97
Related Works: 10
OpenAlex ID: https://openalex.org/W4407370533

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DOI: https://doi.org/10.1021/jacs.4c18423

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Title: Synthesis and Reactivity of an Iron–Tin Complex with Adjacent Stannylidyne and Ferriostannylene Units

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Language: en

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Publication year: 2025

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Publication date: 2025-02-11

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Authors: Yang Liu, Franz F. Westermair, Isabelle Becker, Sebastian Hauer, Michael Bodensteiner, Christoph Hennig, Gábor Balázs, Franc Meyer, Ruth M. Gschwind, Robert Wolf

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Landing page: https://doi.org/10.1021/jacs.4c18423

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Concepts: Chemistry, Tin, Reactivity (psychology), Organic chemistry, Alternative medicine, Pathology, Medicine

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Cited by: 3

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