Bonding Trends in Lewis Acid Adducts of S4N4 – X-ray Structure of TeCl4·S4N4

✍ Scribed by Jari Konu; Tom Bajorek; Risto S. Laitinen; Tristram Chivers; Reijo J. Suontamo; Markku Ahlgrén

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 231 KB
• Volume: 2006
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200600138

✦ Synopsis

Abstract

Tetrasulfur tetranitride and tellurium tetrachloride react in dichloromethane to form a 1:1 adduct TeCl~4~·S~4~N~4~ (1). The crystal structure of 1 shows that TeCl~4~ is bonded to the S~4~N~4~ ring through a Te–N linkage. As a consequence, the transannular S···S bonds in S~4~N~4~ are broken and the molecule assumes an open, monocyclic conformation. The Te–N bond of 2.16(1) Å is slightly longer than the single bond. The S–N bonds span a range of 1.55(1)–1.67(1) Å. The adduct 1 was also characterized by mass spectrometry and Raman spectroscopy. The bonding and spectroscopic properties of 1 are compared by DFT calculations at the B3PW91/(RLC ECP) level of theory with those of BF~3~·S~4~N~4~ (2), SO~3~·S~4~N~4~ (3), AsF~5~·S~4~N~4~ (4), SbCl~5~·S~4~N~4~ (5) for which experimental structural information is available. The structural and bonding trends in TeF~4~·S~4~N~4~ (6), TeBr~4~·S~4~N~4~ (7), and SeX~4~·S~4~N~4~ [X = F (8), Cl (9), Br (10)] are also discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)