Liu, Yang and Westermair, Franz F. and Becker, Isabelle and Hauer, Sebastian and Bodensteiner, Michael and Hennig, Christoph and Balazs, Gabor and Meyer, Franc and Gschwind, Ruth M. and Wolf, Robert (2025) Synthesis and Reactivity of an Iron-Tin Complex with Adjacent Stannylidyne and Ferriostannylene Units. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 147 (8). pp. 7083-7093. ISSN 0002-7863, 1520-5126
Full text not available from this repository. (Request a copy)Abstract
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- i Pr2-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(mu-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(mu-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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CATIONIC METALLOGERMYLENE; ACTIVATION; STANNYLENE; ANALOGS; BONDS; SN; GE; ELIMINATION; REDUCTION; CHEMISTRY |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 23 Jun 2026 05:59 |
| Last Modified: | 23 Jun 2026 05:59 |
| URI: | https://pred.uni-regensburg.de/id/eprint/66358 |
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