Promotion of phosphaalkyne cyclooligomerisation by a Sb(v) to Sb(iii) redox process.

Journal article

A high yield of the tetraphosphaladderene, anti-tetraphosphatricyclo[4.2.0.0(2,5)]octa-3,7-diene, is obtained from reaction of the zirconocene 1,3-diphosphabicyclo[1.1.0]butane with Ph(2)SbCl(3) in THF or CH(2)Cl(2). Exploration of the reaction pathway using density functional theory suggests that an envelope-type adduct of Ph(2)SbCl and 1,3-diphosphabicyclo[1.1.0]butane plays a pivotal role in the reaction. The zwitterionic character of this intermediate species allows it to act simultaneously as both an ene and an eneophile, and a symmetry-allowed bimolecular reaction leads to the tetraphosphaladderene species via a spirocyclic intermediate.

Authors: Fish, C; Green, M; Kilby, R; McGrady, J; Pantazis, D

• Publication status: Published
• Journal: Dalton transactions (Cambridge, England : 2003)
• Issue: 28
• Pages: 3753-3758
• Publication date: 2008-07-01
• DOI: 10.1039/b804401e
• EISSN: 1477-9234
• ISSN: 1477-9226
• Language: English