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Journal Article

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

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Fish, C., Green, M., Kilby, R. J., McGrady, J. E., Pantazis, D. A., & Russell, C. A. (2008). Promotion of phosphaalkyne cyclooligomerisation by a Sb(v) to Sb(iii)redox process. Dalton Transactions, (28), 3753-3758. doi:10.1039/B804401E.

Cite as: https://hdl.handle.net/21.11116/0000-0007-305E-A
A high yield of the tetraphosphaladderene, anti-tetraphosphatricyclo[,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.