Riesinger, Christoph and Meurer, Florian and Zimmermann, Lisa and Duetsch, Luis and Scheer, Manfred (2025) Strain-Release Driven Arsenium Ion Bond Insertion. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 64 (35). ISSN 1521-3773
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Although it marks a cornerstone of pnictogenium ion [R2Pn]+ reactivity, the insertion of arsenium ions [R2As]+ into non-polar bonds remains highly challenging. Herein, a synthetic approach is developed, which circumvents the limitations of insertion reactivity of [R2As]+ (e.g., formal redox state of +V at As) via alleviation of ring strain in the substrate. Thus, unlocking arsenium ion bond insertion delivers the ring-expanded complexes [{LnM}(eta 3-Pn3AsCy2][TEF] ({LnM} = Cp & tprime;Ni, Pn = P (1); {LnM} = {CpMo(CO)2}, Pn = P (2), As (5); Cp & tprime; = 1,2,4-tBu3C5H2, [TEF]- = [Al{OC(CF3)3}4]-). Computational analysis of the reaction mechanism and quantum crystallographic investigation of 1 highlight the release of ring strain as the crucial driving force for this reactivity. This rational is corroborated by the isolation of the arsenium ion coordinated [{CpMo(CO)2}2(mu,eta 2:2-P2AsCy2)][TEF] (3) as well as the phosphenium ion inserted [{CpMo(CO)2}(eta 3-As3PPh2)][TEF] (4).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | HYBRID DENSITY FUNCTIONALS; REACTIVITY; MOLYBDENUM; COMPLEXES; TUNGSTEN; CATIONS; ESTER; Arsenium ion; Bond insertion; Quantum crystallography; Ring strain; Strain-release |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 23 Sep 2026 04:12 |
| Last Modified: | 23 Sep 2026 04:12 |
| URI: | https://pred.uni-regensburg.de/id/eprint/66186 |
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