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Issue 17, 2019
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Bulky cationic β-diketiminate magnesium complexes

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Cationic β-diketiminate Mg complexes with the bulky tBuBDI ligand and the weakly coordinating anion B(C6F5)4 have been prepared by the reaction of (tBuBDI)MgnBu with [Ph3C]+[B(C6F5)4]; tBuBDI = CH[C(tBu)N-Dipp]2 and Dipp = 2,6-diisopropylphenyl. Their structures are compared to the previously reported cationic (MeBDI)Mg+ complexes; MeBDI = CH[C(Me)N-Dipp]2. Crystallization of [(tBuBDI)Mg]+[B(C6F5)4] from chlorobenzene gave a unique (tBuBDI)Mg+·ClC6H5 cation with a rather short Mg⋯Cl and consequently long C–Cl bond. Crystallization from chlorobenzene/arene solvent mixtures gave (tBuBDI)Mg+·arene complexes (arene = benzene, toluene, m-xylene) but in the presence of mesitylene the chlorobenzene complex was formed. Due to the greater shielding of the metal, none of these complexes display Mg⋯(F5C6)4B interactions. Crystal structures of the arene complexes show in all cases η2-coordination of the arene ligands. Ring slippage from a more favorable η2-coordination can be explained by the steric bulk of the tBuBDI ligand. The smaller arenes, benzene and toluene, also bind to (tBuBDI)Mg+ in bromobenzene solution. The Lewis acidity of these cationic Mg complexes was determined by the Gutmann–Beckett test. The acceptor number for (tBuBDI)Mg+ (AN = 76.0) is substantially higher than that estimated for (MeBDI)Mg+ (AN = 70.3). Calculation of the atomic NPA charges by DFT shows that the Mg2+ ion in (tBuBDI)Mg+ is slightly more positively charged than the metal in (MeBDI)Mg+, confirming its higher Lewis acidity. The lower benzene complexation energy calculated for (tBuBDI)Mg+versus (MeBDI)Mg+ is due to steric congestion of the metal in the (tBuBDI)Mg+ cation which allows only for Mg⋯(η1)C6H6 instead of Mg⋯(η6)C6H6 bonding. This ring slippage, however, results in a significant polarization of the electron density in the benzene ring, making it susceptible for nucleophilic attack.

Graphical abstract: Bulky cationic β-diketiminate magnesium complexes

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Publication details

The article was received on 03 Sep 2018, accepted on 06 Dec 2018 and first published on 11 Dec 2018

Article type: Paper
DOI: 10.1039/C8DT03576H
Dalton Trans., 2019,48, 5560-5568

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    Bulky cationic β-diketiminate magnesium complexes

    A. Friedrich, J. Pahl, H. Elsen and S. Harder, Dalton Trans., 2019, 48, 5560
    DOI: 10.1039/C8DT03576H

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