From Missing Links to New Records: A Series of Novel Polychlorine Anions

Abstract

Abstract Herein we report the synthesis and structural characterization of four novel polychloride compounds. The compounds [CCl(NMe 2 ) 2 ][Cl(Cl 2 ) 3 ] and [NPr 4 ][Cl(Cl 2 ) 4 ] have been obtained from the reaction of the corresponding chloride salts with elemental chlorine at low temperature. They are the missing links in the series of polychloride monoanions [Cl(Cl) n ] − ( n =1–6). Additionally, the reaction of decamethylferrocene with elemental chlorine was studied yielding [Cp* 2 Fe] 2 [Cl 20 ], which contains the largest known polychloride [Cl 20 ] 2− to date, and [Cp* 2 Fe][Cl(Cl 2 ) 4 (HF)], which is the first example of a polychloride‐HF network stabilized by strong hydrogen and halogen bonding. All compounds have been characterized by single‐crystal X‐ray diffraction, Raman spectroscopy and quantum‐chemical calculations.