Differing reactivities of PCMe and PCBut towards a triphosphabenzene and a tetraphosphabarrelene: synthesis of new phosphaalkyne pentamers (P5C5MenBut5−n, n = 0, 1 or 2)

Cameron Jones; Christian Schulten; Andreas Stasch

doi:10.1039/B618515K

Differing reactivities of PCMe and PCBu^t towards a triphosphabenzene and a tetraphosphabarrelene: synthesis of new phosphaalkyne pentamers (P₅C₅Me_nBu^t_5−n, n = 0, 1 or 2)

Cameron Jones,*^ab Christian Schulten^ab and Andreas Stasch^ab

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^a School of Chemistry, Monash University, PO Box 23, Melbourne, Victoria, Australia

^b School of Chemistry, Main Building, Cardiff University, Cardiff, UK
E-mail: jonesca6@cardiff.ac.uk

Abstract

The reaction of excess P [triple bond, length as m-dash] CMe with the triphosphabenzene, 1,3,5-P₃C₃Bu^t₃, yields a phosphaalkyne pentamer, P₅C₅Me₂Bu^t₃, which displays a pentaphosphaisolumibullvalene core structure. Its treatment with [W(CO)₅(THF)] gives a complex of this cage, [{W(CO)₅}₂(µ-η¹:η¹-P₅C₅Me₂Bu^t₃)], which has been structurally characterised. In contrast, the previously reported reaction of P [triple bond, length as m-dash] CBu^t with 1,3,5-P₃C₃Bu^t₃, affords, in addition to the known tetraphosphabarrelene, 1,3,5,7-P₄C₄Bu^t₄, a new phosphaalkyne pentamer (P₅C₅Bu^t₅), which has a partially unsaturated “open cage” core. Although PCBu^t does not react with 1,3,5,7-P₄C₄Bu^t₄, the reaction of P [triple bond, length as m-dash] CMe with the tetraphosphabarrelene is shown to give a mixture of products. Treatment of these with [W(CO)₅(THF)] leads to the isolation of the tungsten carbonyl complex, [{W(CO)₅}{W(CO)₄}(µ-η¹:η⁴-P₅C₅MeBu^t₄)], which has been structurally characterised. This study suggests that P [triple bond, length as m-dash] CMe has a significantly greater reactivity towards cycloadditions than its bulkier counterpart, PCBu^t.

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DOI: https://doi.org/10.1039/B618515K
Article type: Paper
Submitted: 19 Dec 2006
Accepted: 09 Mar 2007
First published: 26 Mar 2007

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Dalton Trans., 2007, 1929-1933

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Differing reactivities of PCMe and PCBu^t towards a triphosphabenzene and a tetraphosphabarrelene: synthesis of new phosphaalkyne pentamers (P₅C₅Me_nBu^t_5−n, n = 0, 1 or 2)

C. Jones, C. Schulten and A. Stasch, Dalton Trans., 2007, 1929 DOI: 10.1039/B618515K

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Dalton Transactions

Differing reactivities of PCMe and PCBu^t towards a triphosphabenzene and a tetraphosphabarrelene: synthesis of new phosphaalkyne pentamers (P₅C₅Me_nBu^t_5−n, n = 0, 1 or 2)

Abstract

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Differing reactivities of PCMe and PCBu^t towards a triphosphabenzene and a tetraphosphabarrelene: synthesis of new phosphaalkyne pentamers (P₅C₅Me_nBu^t_5−n, n = 0, 1 or 2)

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