Sodium phosphaethynolate, Na(OCP), as a "P" transfer reagent for the synthesis of N-heterocyclic carbene supported P3 and PAsP radicals

Tondreau, Aaron M., Benkő, Zoltán, Harmer, Jeffrey R. and Grützmacher, Hansjörg (2014) Sodium phosphaethynolate, Na(OCP), as a "P" transfer reagent for the synthesis of N-heterocyclic carbene supported P3 and PAsP radicals. Chemical Science, 5 4: 1545-1554. doi:10.1039/C3SC53140F

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Author Tondreau, Aaron M.
Benkő, Zoltán
Harmer, Jeffrey R.
Grützmacher, Hansjörg
Title Sodium phosphaethynolate, Na(OCP), as a "P" transfer reagent for the synthesis of N-heterocyclic carbene supported P3 and PAsP radicals
Formatted title
Sodium phosphaethynolate, Na(OCP), as a “P” transfer reagent for the synthesis of N-heterocyclic carbene supported P3 and PAsP radicals
Journal name Chemical Science   Check publisher's open access policy
ISSN 2041-6520
2041-6539
Publication date 2014-04-01
Year available 2013
Sub-type Article (original research)
DOI 10.1039/C3SC53140F
Open Access Status DOI
Volume 5
Issue 4
Start page 1545
End page 1554
Total pages 10
Place of publication Cambridge, United Kingdom
Publisher R S C Publications
Language eng
Formatted abstract
Sodium phosphaethynolate, Na(OCP), reacts as a P transfer reagent with the imidazolium salt [DippNHC–H][Cl] [DippNHC = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] to give the parent phosphinidene–carbene adduct, DippNHC=PH, with the loss of CO. In a less atom economic reaction, the cage compound, P7(TMS)3 (TMS = SiMe3) reacts likewise with the imidazolium salt to yield DippNHC=PH thereby giving two entry points into parent phosphinidene-based chemistry. From the building block DippNHC=PH, the carbene-supported P3 cation [(DippNHC)2(μ-P3)][Cl] was rationally synthesized using half an equivalent of PCl3 in the presence of DABCO (1,4-diazabicyclo[2.2.2]octane). The corresponding arsenic analogue, [(DippNHC)2(μ-PAsP)][Cl], was synthesized in the same manner using AsCl3. The reduction of both [(DippNHC)2(μ-P3)][Cl] and [(DippNHC)2(μ-PAsP)][Cl] into their corresponding neutral radical species was achieved simply by reducing the compounds with an excess of magnesium. This allowed the electronic structures of the compounds to be investigated using a combination of NMR and EPR spectroscopy, X-ray crystallography, and computational studies. The findings of the investigation into (DippNHC)2(μ-P3) and (DippNHC)2(μ-PAsP) reveal the central pnictogen atom in both cases as the main carrier of the spin density (~60%), and that they are best described as the P3 or PAsP analogues of the elusive allyl radical dianion. The phosphorus radical was also able to undergo a cycloaddition with an activated acetylene, followed by an electron transfer to give the ion pair [(DippNHC)2(μ-P3)][P3(C(COOMe))2].
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Published online 18 December 2013

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2014 Collection
Centre for Advanced Imaging Publications
 
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Created: Wed, 19 Feb 2014, 04:06:02 EST by Sandrine Ducrot on behalf of Centre for Advanced Imaging