Persulfuration of phosphinines: Synthesis and X-ray crystal structure analysis of a P2S3 derivative

✍ Scribed by Serge Holand; Jean-Marie Alcaraz; Louis Ricard; François Mathey

• Publisher: John Wiley and Sons
• Year: 1990
• Tongue: English
• Weight: 400 KB
• Volume: 1
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.520010106

✦ Synopsis

The reaction of 4,5-dimethyl-2-phenylphosphinine with sulfur in boiling benzene in the presence of Nmethylimiduzole as a catalyst first yields a P-sulfide. This monosulfide further reacts with sulfur to give a diphosphinine trisulfide and a diphosphinine tetrasulfide. The X-ray crystal structure analysis of the trisulfide has been carried out.

The two head-to-tail 1,6-dihydrophosphinine rings are connected by P-S-C and P-C links, thus forming a central I ,2,4-thiadiphospholane heterocycle. The P-C bridge is weak [1.881(3) A] and sulfur can insert into it to give the symmetrical tetrasulfide with two P-S-C bridges.

According to a preliminary study [ 11, the reaction of phosphinines with sulfur initially yields very reactive phosphinine 1-sulfides in which the S 2 1 L aromaticity of the ring appears to have been lost. Since our initial report, phosphinine 1 -sulfides have been generated by thermal decomposition of ' s;%CO2Me S C02Me i, Sx, xylene, reflux; ii, dimethylbutadiene; iii, dimethylacetylene dicarboxylate * To whom correspondence should be addressed.