Promotion of phosphaalkyne cyclooligomerisation by a Sb(V) to Sb(III) redox process

Fish, C., Green, M., Kilby, R. J., McGrady, J. E., Pantazis, D. A. and Russell, C. A. (2008) Promotion of phosphaalkyne cyclooligomerisation by a Sb(V) to Sb(III) redox process. Dalton Transactions(28), pp. 3753-3758. (doi: 10.1039/b804401e)

Abstract

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 Ph2SbCl3 in THF or CH2Cl2. Exploration of the reaction pathway using density functional theory suggests that an envelope-type adduct of Ph2SbCl 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.

• Item Type: Articles
• Keywords: 1,3,5,7-TETRAPHOSPHABARRELENE 1,3-DIPHOSPHACYCLOBUTADIENE CAGE COMPOUND COMPLEXES CORRELATED MOLECULAR CALCULATIONS DENSITY Density functional theory GAUSSIAN-BASIS SETS ORGANOPHOSPHORUS COMPOUNDS PATHWAY PHOSPHORUS-COMPOUNDS PSEUDOPOTENTIALS REDOX UNUSUAL COORDINATION
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Pantazis, Dr Dimitrios and McGrady, Prof John
• Authors: Fish, C., Green, M., Kilby, R. J., McGrady, J. E., Pantazis, D. A., and Russell, C. A.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Dalton Transactions
• ISSN: 1477-9226