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Beyond the limit: Investigation of large polychloride anions [Cl₁₁]⁻, [Cl₁₂]²⁻ and [Cl₁₃]⁻

Karsten Sonnenberg, Patrick Pröhm, Nico Schwarze, Carsten Müller, Helmut Beckers and Sebastian Riedel – 2018

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 [NMe₃Ph]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.

Titel
Beyond the limit: Investigation of large polychloride anions [Cl₁₁]⁻, [Cl₁₂]²⁻ and [Cl₁₃]⁻
Verfasser
Karsten Sonnenberg, Patrick Pröhm, Nico Schwarze, Carsten Müller, Helmut Beckers and Sebastian Riedel
Schlagwörter
Halogens • Polychlorides • Quantum-chemical calculations • Halogen-bonding • X-ray structure
Datum
2018
Erschienen in
Angew. Chem. Int. Ed. 2018, 9136-9140
Zitierweise
DOI: 10.1002/anie.201803486 (Int. Ed.); 10.1002/ange.201803486
Sprache
eng