Novel Coordination Modes for E4S3 Cage Molecules (E = P, As) in Unprecedented Quaternary As4S3(CuCl)n (n = 1,2) Solid-State Phases

✍ Scribed by Patrick Schwarz; Joachim Wachter; Manfred Zabel

• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 273 KB
• Volume: 2008
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200801015

✦ Synopsis

Abstract

First examples of the coordination chemistry of the As~4~S~3~ cage were obtained from solutions of As~4~S~3~·M(CO)~5~ (M = Cr, W) in CH~2~Cl~2~ and CuCl__~n~__ in CH~3~CN (n = 1) or CH~3~OH (n = 2) through interdiffusion techniques. The compounds (As~4~S~3~)(CuCl)~n~ (1: n = 1; 2: n = 2) exhibit Cu coordination exclusively through the sulfur bridges. The crystal structure of 1 containsa saw‐like [CuCl] backbone to which As~4~S~3~ cages are alternately fixed on both sides through two of their sulfur atoms. The crystal structure of 2 is built up of sheets, in which As~4~S~3~ molecules are connected by folded four‐membered Cu~2~Cl~2~ rings through all sulfur atoms. Comparative Raman spectra of As~4~S~3~ and 1 indicate significant interactions between the cage S atoms and Cu.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)