Investigation of Large Polychloride Anions: [Cl11 ]- , [Cl12 ]2- , and [Cl13 ].

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, [Cl8 ]2- , polychlorine compounds such as polychloride anions are unknown. Herein, we report on the synthesis and investigation of large polychloride monoanions such as [Cl11 ]- found in [AsPh4 ][Cl11 ], [PPh4 ][Cl11 ], and [PNP][Cl11 ]⋅Cl2 , and [Cl13 ]- obtained in [PNP][Cl13 ]. The polychloride dianion [Cl12 ]2- has been obtained in [NMe3 Ph]2 [Cl12 ]. 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.