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Issue 99, 2014
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From MgBr via single-electron transfer (SET) to a paramagnetic Mg(II) compound and back to Mg(I): [MgBr(L1)˙]2 and [K(thf)3]2[Mg2(L1)2], L1 = RN[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]NR, R = 2,6-diisopropylphenyl

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Abstract

Since Mg+ ions are isoelectronic to Na atoms, an easy single electron transfer (SET) can be expected for MgBr. Even at 190 K, the radical MgBr (obtained via its sophisticated condensation) in a metastable solution transfers its electron to a diazadiene entity. A paramagnetic Mg(II) compound [MgBr(L1)˙]2 (4; L1 = DippN[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]NDipp) is formed consisting of a singly reduced ligand. As shown by EPR investigations, dimeric 4 dissociates in ethereal solvents to two monomeric subunits. In addition, 4 can subsequently be reduced with potassium to furnish again a Mg(I) compound, namely [K(thf)3]2[Mg2(L1)2] (3).

Graphical abstract: From MgBr via single-electron transfer (SET) to a paramagnetic Mg(ii) compound and back to Mg(i): [MgBr(L1)˙]2 and [K(thf)3]2[Mg2(L1)2], L1 = RN [[double bond, length as m-dash]] C(Me)C(Me) [[double bond, length as m-dash]] NR, R = 2,6-diisopropylphenyl

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Publication details

The article was received on 06 Oct 2014, accepted on 23 Oct 2014 and first published on 30 Oct 2014


Article type: Communication
DOI: 10.1039/C4CC07680J
Citation: Chem. Commun., 2014,50, 15677-15680

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    From MgBr via single-electron transfer (SET) to a paramagnetic Mg(II) compound and back to Mg(I): [MgBr(L1)˙]2 and [K(thf)3]2[Mg2(L1)2], L1 = RN[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]NR, R = 2,6-diisopropylphenyl

    T. Kruczyński, P. Henke, T. Augenstein, N. Arleth, F. Breher and H. Schnöckel, Chem. Commun., 2014, 50, 15677
    DOI: 10.1039/C4CC07680J

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