Abstract
Preference for the binding mode of the CN− ligand to Mg (Mg−CN vs. Mg−NC) is investigated. A monomeric Mg complex with a terminal CN ligand was prepared using the dipyrromethene ligand MesDPM which successfully blocks dimerization. While reaction of (MesDPM)MgN(SiMe3)2 with Me3SiCN gave the coordination complex (MesDPM)MgN(SiMe3)2⋅NCSiMe3, reaction with (MesDPM)Mg(nBu) led to (MesDPM)MgNC⋅(THF)2. A Mg−NC/Mg−CN ratio of ≈95:5 was established by crystal‐structure determination and DFT calculations. IR studies show absorbances for CN stretching at 2085 cm−1 (Mg−NC) and 2162 cm−1 (Mg−CN) as confirmed by 13C labeling. In solution and in the solid state, the CN ligand rotates within the pocket. The calculated isomerization barrier is only 12.0 kcal mol−1 and the 13C NMR signal for CN decoalesces at −85 °C (Mg−NC: 175.9 ppm, Mg−CN: 144.3 ppm). Experiment and theory both indicate that Mg complexes with the CN− ligand should not be named cyanides but are more properly defined as isocyanides.
Highlights
Preference for the binding mode of the CNÀ ligand to Mg (MgÀCN vs. MgÀNC) is investigated
The calculated isomerization barrier is only 12.0 kcal molÀ1 and the 13C NMR signal for CN decoalesces at À85 8C (MgÀNC: 175.9 ppm, MgÀCN: 144.3 ppm). Experiment and theory both indicate that Mg complexes with the CNÀ ligand should not be named cyanides but are more properly defined as isocyanides
Experimental and calculation data indicate that the XÀCN/XÀNC ratio increases with increasing electronegativity of X, that is, the cyanide isomer becomes more favorable for covalently bound CN groups (Scheme 1 a).[13–18]
Summary
Preference for the binding mode of the CNÀ ligand to Mg (MgÀCN vs. MgÀNC) is investigated. A MgÀNC/MgÀCN ratio of % 95:5 was established by crystal-structure determination and DFT calculations.
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