Diverse Reactivity of a Ca(I) Synthon

Mai J, Rösch B, Langer J, Grams S, Morasch M, Harder S (2023)

Publication Type: Journal article

Publication year: 2023

Journal

DOI: 10.1002/ejic.202300421

Abstract

Low-valent Mg^I complexes like (BDI)Mg−Mg(BDI) have found wide-spread application as specialty reducing agents (BDI=β-diketiminate). Also their redox reactivity was extensively investigated. In contrast, attempts to isolate similar Ca^I complexes led to reduction of the aromatic solvents or N2. Complex (^DIPePBDI)Ca(μ6,μ6-C6H6)Ca(^DIPePBDI) (VIII) should be regarded a Ca^II complex with a bridging C6H6²⁻ dianion (^DIPePBDI=HC[C(Me)N-DIPeP]2, DIPeP=2,6-C(H)Et2-phenyl). It can react as a Ca^I synthon by releasing benzene and two electrons. Herein we describe the reactivity of VIII with benzene, biphenyl, naphthalene, anthracene, COT, Ph3SiCl, PhSiH3, a (BDI)AlI2 complex, H2, PhX (X=F, Cl, Br, I), tBuOH and tBuCH2I. The C6H6²⁻ dianion in VIII can react as a 2e⁻ source, a nucleophile or a Brønsted base. In some cases radical reactivity cannot be excluded. Crystal structures of (^DIPePBDI)Ca(μ8,μ8-COT)Ca(^DIPePBDI) (1) and [(^DIPePBDI)CaX ⋅ (THF)]2 (X=F, Cl, Br, I) (2–5) are described.

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How to cite

APA:

Mai, J., Rösch, B., Langer, J., Grams, S., Morasch, M., & Harder, S. (2023). Diverse Reactivity of a Ca(I) Synthon. European Journal of Inorganic Chemistry. https://doi.org/10.1002/ejic.202300421

MLA:

Mai, Jonathan, et al. "Diverse Reactivity of a Ca(I) Synthon." European Journal of Inorganic Chemistry (2023).

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