TRISPHAT

TRISPHAT (full name tris(tetrachlorocatecholato)phosphate(1−)) is an inorganic anion with the formula P(O
2C
6Cl
4)−
3 often prepared as the tributylammonium ((C
4H
9)
3NH+
) or tetrabutylammonium ((C
4H
9)
4N+
 salt. The anion features phosphorus(V) bonded to three tetrachlorocatecholate (C
6Cl
4O2−
2) ligands. This anion can be resolved into the axially chiral enantiomers, which are optically stable (the picture shows the Δ enantiomer).

TRISPHAT
Names
IUPAC name
Tetrabutylammonium tris(3,4,5,6-tetrachlorobenzene-1,2-diolato-κ2O1,O2)phosphorus(V)
Other names
Tetrabutylammonium tris(tetrachlorocatecholato)phosphorus(1−)
Bu4N+ PHAT−
1-Butanaminium, N,N,N-tributyl-, (OC-6-11-Δ)-tris[3,4,5,6-tetrachloro-1,2-benzenediolato(2-)-κO1,κO2]phosphate(1−) (1:1)
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.164.647
EC Number
  • tetrabutylammonium salt:: 636-891-3
  • tetrabutylammonium salt:: InChI=1S/C18Cl12O6P.C16H36N/c19-1-2(20)8(26)14-13(7(1)25)31-37(32-14,33-15-9(27)3(21)4(22)10(28)16(15)34-37)35-17-11(29)5(23)6(24)12(30)18(17)36-37;1-5-9-13-17(14-10-6-2,15-11-7-3)16-12-8-4/h;5-16H2,1-4H3/q-1;+1
    Key: GCGVBYHPNKLLAV-UHFFFAOYSA-N
  • O1c0c(Cl)c(Cl)c(Cl)c(Cl)c0O[P-]123(Oc0c(Cl)c(Cl)c(Cl)c(Cl)c0O2)Oc0c(Cl)c(Cl)c(Cl)c(Cl)c0O3
  • tributylammonium salt:: O1c0c(Cl)c(Cl)c(Cl)c(Cl)c0O[P-]123(Oc0c(Cl)c(Cl)c(Cl)c(Cl)c0O2)Oc0c(Cl)c(Cl)c(Cl)c(Cl)c0O3.CCCC[N+H](CCCC)CCCC
  • tetrabutylammonium salt:: CCCC[N+](CCCC)(CCCC)CCCC.C12=C(C(=C(C(=C1Cl)Cl)Cl)Cl)O[P-]34(O2)(OC5=C(O3)C(=C(C(=C5Cl)Cl)Cl)Cl)OC6=C(O4)C(=C(C(=C6Cl)Cl)Cl)Cl
Properties
[C16H36N][C18Cl12O6P]
Molar mass 1011.06
Appearance colourless solid
CH2Cl2
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

The TRISPHAT anion has been used as a chiral shift reagent for cations.[1] It improves the resolution of 1H NMR spectra by forming diastereomeric ion pairs.

Preparation

The anion is prepared by treatment of phosphorus pentachloride with tetrachlorocatechol followed by a tertiary amine gives the anion:

PCl5 + 3 C6Cl4(OH)2 → H[P(O2C6Cl4)3] + 5 HCl
H[P(O2C6Cl4)3] + Bu3N → Bu3NH+ [P(O2C6Cl4)3]−

Using a chiral amine, the anion can be readily resolved.[2]

References
  1. Ratni, Hassen; Jodry, Jonathan J.; Lacour, Jérôme; Kündig, E. Peter (2000). "[n-Bu4N][Δ-TRISPHAT] Salt, an Efficient NMR Chiral Shift Reagent for Neutral Planar Chiral Tricarbonylchromium Complexes". Organometallics. 19 (19): 3997–3999. doi:10.1021/om000437f.
  2. Favarger, France; Goujon-Ginglinger, Catherine; Monchaud, David; Lacour, Jérôme (2004). "Large-Scale Synthesis and Resolution of TRISPHAT [Tris(tetrachlorobenzenediolato) Phosphate(V)] Anion". Journal of Organic Chemistry. 69 (24): 8521–8524. doi:10.1021/jo048641q. PMID 15549835..
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