Polychloride monoanions from [Cl3]- to [Cl9]- : a Raman spectroscopic and quantum chemical investigation

Polychloride monoanions stabilized by quaternary ammonium salts are investigated using Raman spectroscopy and state-of-the-art quantum-chemical calculations. A regular V-shaped pentachloride is characterized for the N(Me)(4)]Cl(5)] salt, whereas a hockey-stick-like structure is tentatively assigned for N(Et)(4)]Cl(2)???Cl(3)(-)]. Increasing the size of the cation to the quaternary ammonium salts NPr(4)](+) and NBu(4)](+) leads to the formation of the Cl(3)](-) anion. The latter is found to be a pale yellow liquid at about 40 °C, whereas all the other compounds exist as powders. Further to these observations, the novel Cl(9)](-) anion is characterized by low-temperature Raman spectroscopy in conjunction with quantum-chemical calculations.