Investigation of Large Polychloride Anions: [Cl11]−, [Cl12]2−, and [Cl13]−. Issue 29 (21st June 2018)

• Record Type: Journal Article
• Authors: Sonnenberg, Karsten; Pröhm, Patrick; Schwarze, Nico; Müller, Carsten; Beckers, Helmut; Riedel, Sebastian
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 29(2018)
• Page Start: 9136
• Page End: 9140
• Publication Date: 2018-06-21
• Subjects: halogen bonding -- halogens -- polychlorides -- X-ray diffraction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201803486
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : Polyiodides and ‐bromides are far more common than their chloride counterparts. Salts of large polychloride monoanions such as [Cl11 ] − and [Cl13 ] − have been synthesized and investigated, along with a salt of the polychloride dianion [Cl12 ] 2− . The dianions in [NMe3 Ph]2 [Cl12 ] form a three‐dimensional network with a honeycomb‐like arrangement.