Nova Complexes or Rhodium(I) Containing Bridging SO2 Ligands

✍ Scribed by Martin Cowie; Stephen K Dwight; Alan R Sanger

• Publisher: Elsevier Science
• Year: 1978
• Tongue: English
• Weight: 301 KB
• Volume: 31
• Category: Article
• ISSN: 0020-1693
• DOI: 10.1016/s0020-1693(00)94940-5

✦ Synopsis

The recently reported complex, [l] [Rh,(CO)2-(/+&O)(@)(DPM),]

BPh4, (l), (DPM = bis(diphenylphosphino)methane; Ph = CsHs), is the first structurally characterized example of an "A-frame" complex containing a ligand in the proposed "active site", bridging the two metal atoms. This carbonylbridged cationic complex is obtained by the reversible addition of CO to the parent complex, [Rh(CO)2-(p-Cl)(DPM),] BPh,, (2) and conclusively establishes that small molecules can coordinate to the active site in "A-frame" complexes as first suggested by Kubiak and Eisenberg . We wish now to report the reaction of SOz with 2, which yields initially the SOzadduct, believed to be analogous to the CO-bridged complex, 1. In addition, however, a variety of new and interesting chemistry is observed. The crystal structure of one of the products in this reaction is also reported.

Treatment of an acetone or dichloromethane solution of 2 with SO* gave initially a red solution. Addition of petroleum ether or slow evaporation of the solvent gave a red-brown crystalline product, [Rh?-