Reduction reactions of a 1,3,5-triphosphabenzene

Cameron Jones, Mark Waugh

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The reactions of the triphosphabenzene, 1,3,5-P3C3But3, with LiMH4, M = Al or Ga, lead to the triphosphabicyclo[3.1.0]hexanediyl metallate complexes, [([Li(OEt2)][MH2(P3C3But3H2)])2], which give exo- and endo-isomers of a triphosphabicyclo[3.1.0]hexane, P3C3But3H4upon quenching. The related reaction of [AlH3(NMe3)] with 1,3,5-P3C3But3affords three identifiable products, viz. a triphosphabicyclo[3.1.0]hexenyl complex, [AlH2(P3C3But3H)(NMe3)], and two triphosphabicyclo[3.1.0]hexanediyl complexes, [AlH(P3C3But3H2)(NMe3)] and [Al2H4(P3C3But3H2)(NMe3)]. In contrast, the reactions of 1,3,5-P3C3But3with either [GaH3(quin)], quin = quinuclidine, or Me3SnH lead only to the triphosphabicyclo[3.1.0]hexenyl complexes, [GaH2(P3C3But3H)(quin)] and [Me3Sn(P3C3But3H)]. Quenching of the former affords a triphosphabicyclo[3.1.0]hexene, P3C3But3H2, while quenching the latter gives its triphosphacyclohexa-1,4-diene valence isomer. Treatment of 1,3,5-P3C3But3with “GaI” yields a GaI3complex of the triphosphahexa-1,4-diene, [GaI3(P3C3But3H2)], whilst treatment with the anionic Ga(i) heterocycle, [:Ga(N(Ar)C(H))2]−, Ar = C6H3Pri2-2,6, affords the known diphospholyl anion, [1,3-P2C3But3]−via a P-abstraction from the triphosphabenzene. Finally, reaction of the 1,3,5-triphosphacyclohexane, (P(OEt)C(H)(But))3, with thionyl chloride yields the unusual λ555-1,3,5-triphosphacyclohexane, (P(O)(Cl)C(H)(But))2(P(OEt)(S)C(H)(But)). Suggestions as to the mechanisms of a number of these reduction reactions are made and the crystal structures of seven compounds are reported.

Original languageEnglish
Pages (from-to)1971-1979
Number of pages9
JournalDalton Transactions
Issue number13
Publication statusPublished - 28 Jun 2004


  • Group 13
  • Group 15
  • Heterocycles
  • Hydrides
  • P-containing ligands

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