Investigation of Large Polychloride Anions: [Cl-11](-), [Cl-12](2-), and [Cl-13](-)

摘要

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 [AsPh4][Cl-11], [PPh4][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 [NMe3Ph](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.