CPh3 as a functional group in P-heterocyclic chemistry: elimination of HCPh3 in the reaction of P-CPh3 substituted Li/Cl phosphinidenoid complexes with Ph2CO12. Issue 6 (11th January 2016)

• Record Type: Journal Article
• Authors: García, C. Murcia; Ferao, A. Espinosa; Schnakenburg, G.; Streubel, R.
• Is Part Of: Dalton transactions. Volume 45:Issue 6(2016)
• Page Start: 2378
• Page End: 2385
• Publication Date: 2016-01-11
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt04595a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Li/Cl phosphinidenoid complexes2a–c react with benzaldehyde to give3a–c, but with benzophenone formation of complexes4 and5 was observed, the latter revealing the elimination of HCPh3 . Abstract : P -CPh3 substituted oxaphosphirane complexes3 were prepared using Li/Cl phosphinidenoid complexes2 (M = Cr, Mo, W) and benzaldehyde. Employing2 and benzophenone resulted in the formation of oxaphospholane complexes4 and5, the former bearing a benzo[ c ]-1, 2-oxaphospholane and the latter a novel pentacyclic P-ligand. According to DFT studies the latter P-heterocycle arises from formal dimerization of a transient benzofused 2-phosphafurane complex8, one of the fragments undergoing water-catalyzed [1, 3]H shift (4 ) and the other (11 ) formed via elimination of HCPh3 .