Synthesis of cationic R2P5 + cages and subsequent chalcogenation reactions

Holthausen M.H., Hepp A., Weigand J.J.

Abstract

Cationic R2P5+ cage compounds (1 +) have been synthesized by the stoichiometric reaction of R 2PCl, GaCl3 and P4. The reaction conditions depend on the substituent R. Alkyl-substituted derivatives (1 a-1 d[GaCl 4]) are best synthesized under solvent-free conditions, whereas aryl-substituted derivatives (1 e-1 h[GaCl4]) are formed in C 6H5F. All compounds have been prepared on a multi-gram scale in good to excellent yields and have been fully characterized with an emphasis on 31P NMR spectroscopy in solution and single-crystal structure determination. Subsequent chalcogenation reactions of cations R 2P5+ (1 a+, 1 e+) and trication Ph6P73+ (33+) with elemental sulfur (α-S8) or grey selenium (Segrey) yielded a series of unique polyphosphorus-chalcogen cations (4 a+, 4 e+, 5 a+, 62+ and 72+ Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.