Towards Naked Zinc(II) in the Condensed Phase: A Highly Lewis Acidic Zn<sup>II</sup> Dication Stabilized by Weakly Coordinating Carborate Anions
Nicolas Adet, David Specklin, Christophe Gourlaouen, Thibault Damiens, Béatrice Jacques, Rudolf J. Wehmschulte, Samuel Dagorne
Abstract
Abstract The employment of the hexyl‐substituted anion [HexCB 11 Cl 11 ] − allowed the synthesis of a Zn II species, Zn[HexCB 11 Cl 11 ] 2 , 3 , in which the Zn 2+ cation is only weakly coordinated to two carborate counterions and that is soluble in low polarity organic solvents such as bromobenzene. DOSY NMR studies show the facile displacement of at least one of the counterions, and this near nakedness of the cation results in high catalytic activity in the hydrosilylation of 1‐hexene and 1‐methyl‐1cyclohexene. Fluoride ion affinity (FIA) calculations reveal a solution Lewis acidity of 3 (FIA=262.1 kJ mol −1 ) that is higher than that of the landmark Lewis acid B(C 6 F 5 ) 3 (FIA=220.5 kJ mol −1 ). This high Lewis acidity leads to a high activity in catalytic CO 2 and Ph 2 CO reduction by Et 3 SiH and hydrogenation of 1,1‐diphenylethylene using 1,4‐cyclohexadiene as the hydrogen source. Compound 3 was characterized by multinuclear NMR spectroscopy, mass spectrometry, single crystal X‐ray diffraction, and DFT studies.