Investigation of Large Polychloride Anions: [Cl 11 ] − , [Cl 12 ] 2− , and [Cl 13 ] −

For decades the chemistry of polyhalides was dominated by polyiodides and more recently also by an increasing number of polybromides. However, apart from a few structures containing trichloride anions and a single report on an octachloride dianion, [Cl 8 ] 2− , polychlorine compounds such as polychloride anions are unknown. Herein, we report on the synthesis and investigation of large polychloride monoanions such as [Cl 11 ] − found in [AsPh 4 ][Cl 11 ], [PPh 4 ][Cl 11 ], and [PNP][Cl 11 ]⋅Cl 2 , and [Cl 13 ] − obtained in [PNP][Cl 13 ]. The polychloride dianion [Cl 12 ] 2− has been obtained in [NMe 3 Ph] 2 [Cl 12 ]. The novel compounds have been thoroughly characterized by NMR spectroscopy, single‐crystal Raman spectroscopy, and single‐crystal X‐ray diffraction. The assignment of their spectra is supported by molecular and periodic solid‐state quantum‐chemical calculations.