A mechanistic study of the c-p bond cleavage reaction of 1,2-(ph2)(2)-c6h4 with (buli)-bu-n/sb(nme2)(3)

R. Edge, R.J. Less, V. Naseri, E.J.L. McInnes, R.E. Mulvey, D.S. Wright

Research output: Contribution to journalArticle

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Abstract

In situ 31P NMR spectroscopic studies of the reaction of the primary diphosphine 1,2-(PH2)2-C6H4 with the mixed-metal base system nBuLi/Sb(NMe2)3, combined with X-ray structural investigations, strongly support a mechanism involving a series of deprotonation steps followed by antimony-mediated reductive C-P bond cleavage. The central intermediate in this reaction is the tetraphosphide dianion [C6H4P2]22- ([4]) from which the final products, the 1,2,3-triphospholide anion [C6H4P3]- (3) and [PhPHLi] (8·Li), are evolved. An EPR spectrocopic study suggests that homolytic C-P bond cleavage is likely to be involved in this final step.
LanguageEnglish
Pages6454-6460
Number of pages6
JournalDalton Transactions
Issue number45
DOIs
Publication statusPublished - 2008

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Antimony
Deprotonation
Anions
Paramagnetic resonance
Metals
Nuclear magnetic resonance
X rays

Keywords

  • spectroscopic studies
  • c-p bond cleavage

Cite this

Edge, R. ; Less, R.J. ; Naseri, V. ; McInnes, E.J.L. ; Mulvey, R.E. ; Wright, D.S. / A mechanistic study of the c-p bond cleavage reaction of 1,2-(ph2)(2)-c6h4 with (buli)-bu-n/sb(nme2)(3). In: Dalton Transactions. 2008 ; No. 45. pp. 6454-6460.
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A mechanistic study of the c-p bond cleavage reaction of 1,2-(ph2)(2)-c6h4 with (buli)-bu-n/sb(nme2)(3). / Edge, R.; Less, R.J.; Naseri, V.; McInnes, E.J.L.; Mulvey, R.E.; Wright, D.S.

In: Dalton Transactions, No. 45, 2008, p. 6454-6460.

Research output: Contribution to journalArticle

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T1 - A mechanistic study of the c-p bond cleavage reaction of 1,2-(ph2)(2)-c6h4 with (buli)-bu-n/sb(nme2)(3)

AU - Edge, R.

AU - Less, R.J.

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AU - Wright, D.S.

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AB - In situ 31P NMR spectroscopic studies of the reaction of the primary diphosphine 1,2-(PH2)2-C6H4 with the mixed-metal base system nBuLi/Sb(NMe2)3, combined with X-ray structural investigations, strongly support a mechanism involving a series of deprotonation steps followed by antimony-mediated reductive C-P bond cleavage. The central intermediate in this reaction is the tetraphosphide dianion [C6H4P2]22- ([4]) from which the final products, the 1,2,3-triphospholide anion [C6H4P3]- (3) and [PhPHLi] (8·Li), are evolved. An EPR spectrocopic study suggests that homolytic C-P bond cleavage is likely to be involved in this final step.

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