TRISPHAT

{{chembox

| verifiedrevid = 424874343

| ImageFileL1 = Trisphat.png

| ImageSizeL1 = 170

| ImageFileR1 = Delta-TRISPHAT-3D-balls.png

| ImageSizeR1 = 170

| IUPACName = Tetrabutylammonium tris(3,4,5,6-tetrachlorobenzene-1,2-diolato-κ2O1,O2)phosphorus(V)

| OtherNames = 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)

|Section1={{Chembox Identifiers

| CASNo2_Ref = {{cascite|correct|CAS}}

| CASNo2 = 301687-57-0

| index1_label = tributylammonium salt:

| index2_label = tetrabutylammonium salt:

| ChemSpiderID2 = 35467078

| DTXSID2 = DTXSID80746191

| EC_number2 = 636-891-3

| PubChem2 = 71310446

| SMILES = 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

| SMILES1 = 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

| InChI2=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

| InChIKey2 = GCGVBYHPNKLLAV-UHFFFAOYSA-N

| SMILES2 = 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

}}

|Section2={{Chembox Properties

| Formula = [C16H36N][C18Cl12O6P]

| MolarMass = 1011.06

| Appearance = colourless solid

| Density =

| MeltingPt =

| BoilingPt =

| Solubility = CH2Cl2

}}

|Section3={{Chembox Hazards

| MainHazards =

| FlashPt =

| AutoignitionPt =

}}

}}

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

The TRISPHAT anion has been used as a chiral shift reagent for cations.{{cite journal | first1=Hassen | last1=Ratni | first2=Jonathan J. | last2=Jodry | first3=Jérôme | last3=Lacour | first4=E. Peter | last4=Kündig | title=[n-Bu4N][Δ-TRISPHAT] Salt, an Efficient NMR Chiral Shift Reagent for Neutral Planar Chiral Tricarbonylchromium Complexes | journal=Organometallics | year=2000 | volume=19 | issue=19 | pages=3997–3999 | doi=10.1021/om000437f}} 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.{{cite journal | first1=France | last1=Favarger | first2=Catherine | last2=Goujon-Ginglinger | first3=David | last3=Monchaud | first4=Jérôme | last4=Lacour | title=Large-Scale Synthesis and Resolution of TRISPHAT [Tris(tetrachlorobenzenediolato) Phosphate(V)] Anion | journal=Journal of Organic Chemistry | year=2004 | volume=69 | issue=24 | pages=8521–8524 | doi=10.1021/jo048641q| pmid=15549835 }}.

References