Wikipedia:WikiProject Chemicals/Chembox validation/VerifiedDataSandbox and Tetraphenylphosphonium chloride: Difference between pages

| Verifiedfields = changed

| Watchedfields = changed

| verifiedrevid = 470605013

| ImageSize = 150px

| PIN = Tetraphenylphosphanium chloride

|Section1={{Chembox Identifiers

| CASNo_Ref = {{cascite|correct|CAS}}

| CASNo = 2001-45-8

| EINECS = 217-890-3

}}

|Section2={{Chembox Properties

| Formula = {{chem2|[P(C6H5)4]Cl}}

| C=24|H=20|Cl=1|P=1

| Density = 1.27 g dm⁻³

| MeltingPtC = 272 to 274

| MeltingPt_notes =

| BoilingPt_notes =

| Solubility =

|Section7={{Chembox Hazards

| NFPA-S =

| GHS_ref=<ref>{{cite web |title=Tetraphenylphosphonium chloride |url=https://pubchem.ncbi.nlm.nih.gov/compound/164911#section=Safety-and-Hazards |website=pubchem.ncbi.nlm.nih.gov |access-date=12 December 2021 |language=en}}</ref>

| GHSPictograms = {{GHS07}}

| GHSSignalWord = Warning

| HPhrases = {{H-phrases|315|319|335}}

| PPhrases = {{P-phrases|261|264|271|280|302+352|304+340|305+351+338|312|321|332+313|337+313|362|403+233|405|501}}

| AutoignitionPt =

| PEL =

}}

'''Tetraphenylphosphonium chloride''' is the chemical compound with the formula {{chem2|[(C6H5)4P]Cl}}, abbreviated {{chem2|Ph4PCl}} or {{chem2|PPh4Cl}} or {{chem2|[PPh4]Cl}}, where Ph stands for [[phenyl]]. Tetraphenylphosphonium and especially tetraphenylarsonium salts were formerly of interest in [[gravimetric analysis]] of [[perchlorate]] and related oxyanions. This colourless [[salt (chemistry)|salt]] is used to generate lipophilic salts from inorganic and organometallic [[anion]]s. Thus, {{chem2|[Ph4P]+}} is useful as a [[phase-transfer catalyst]], again because it allows inorganic anions to dissolve in [[organic solvent]]s.

==Structure and basic properties==

The structure of this salt is {{chem2|[PPh4]+Cl−}}. It consists of tetraphenylphosphonium [[cations]] {{chem2|[PPh4]+}} and [[chloride]] [[anions]] {{chem2|Cl−}}. The {{chem2|[PPh4]+}} cation is [[tetrahedral molecular geometry|tetrahedral]].

PPh₄Cl crystallises as the [[anhydrous]] salt,<ref>{{cite journal|first1=J. F. |last1=Richardson |first2=J. M. |last2=Ball |first3=P. M. |last3=Boorman |title=Structure of Tetraphenylphosphonium Chloride |journal=Acta Crystallographica |date=1986 |volume=C42 |issue=9 |pages=1271–1272 |doi=10.1107/S0108270186092612|bibcode=1986AcCrC..42.1271R }}</ref> which is the normal item of commerce, as well as a [[monohydrate]]<ref>{{cite journal|first1=E. E. |last1=Schweizer |first2=C. J. |last2=Baldacchini |first3=A. L. |last3=Rheingold |title=Tetraphenylphosphonium Chloride Monohydrate, Tetraphenylphosphonium Bromide and Tetraphenylphosphonium Iodide |journal=Acta Crystallographica |date=1989 |volume=C45 |issue=8 |pages=1236–1239 |doi=10.1107/S0108270189000363|bibcode=1989AcCrC..45.1236S }}</ref> and a dihydrate.<ref>{{cite journal|first1=A. J. |last1=Blake |first2=C. D. |last2=Garner |first3=J. M. |last3=Tunney |title=Tetraphenylphosphonium Chloride Dihydrate |journal=Acta Crystallographica |date=2003 |volume=E59 |issue=1 |page=o9–o10 |doi=10.1107/S1600536802021682|bibcode=2003AcCrE..59O...9B }}</ref>

In [[X-ray crystallography]], {{chem2|PPh4+}} salts are of interest as they often crystallise easily. The rigidity of the phenyl groups facilitates packing and elevates the [[melting point]] relative to alkyl-based [[quaternary ammonium salt]]s. Also, since these salts are soluble in organic media, a wide range of solvents can be employed for their crystallisation.

{| class="wikitable" style="margin:1em auto; text-align:center;"

| [[File:Tetraphenylphosphonium-chloride-from-xtal-3D-SF.png|150px]]||[[File:Tetraphenylphosphonium-chloride-xtal-3D-SF.png|200px]]||[[File:Tetraphenylphosphonium-chloride-xtal-3D-balls.png|200px]]

|-

| <small>constituent ions in the solid</small>||<small>[[space-filling model]] of part<br>of the [[crystal structure]]</small>||<small>[[ball-and-stick model]] of part<br>of the crystal structure</small>

|}

==Preparation==

{{chem2|[PPh4]Cl}} and many analogous compounds can be prepared by the reaction of [[chlorobenzene]] with [[triphenylphosphine]] catalysed by nickel salts:<ref>{{cite journal|first1=David |last1=Marcoux |first2=André B. |last2=Charette |title=Nickel-Catalyzed Synthesis of Phosphonium Salts from Aryl Halides and Triphenylphosphine |journal=Adv. Synth. Catal. |date=2008 |volume=350 |issue=18 |pages=2967–2974 |doi=10.1002/adsc.200800542}}</ref>

:{{chem2|PhCl + PPh3 → [Ph4P]Cl}}

The compound was originally prepared as the corresponding bromide salt (CAS No. 2751-90-8), which in turn was synthesized by passing dry oxygen through the reaction of [[phenylmagnesium bromide]] and [[triphenylphosphine]].<ref>{{cite journal|last1=Dodonow |first1=J. |last2=Medox |first2=H. |title=Zur Kenntnis der Grignardschen Reaktion: Über die Darstellung von Tetraphenyl-phosphoniumsalzen |journal=Berichte der Deutschen Chemischen Gesellschaft |date=1928 |volume=61 |issue=5 |pages=907–911 |doi=10.1002/cber.19280610505}}</ref> The synthesis probably proceeds via the reaction of the [[Grignard reagent]] with [[triphenylphosphine oxide]].

:{{chem2|PhMgBr + Ph3PO → [Ph4P]OMgBr}}

:{{chem2|[Ph4P]OMgBr + HBr → [Ph4P]Br + "Mg(OH)Br"}}

==Use in synthesis==

Tetraphenylphosphonium salts of inorganic or organometallic anions are often sought because they are easily crystallized. They also tend to be soluble in polar organic solvents such as [[acetonitrile]] and [[dimethylformamide]]. Examples include the tetraphenylphosphonium [[perrhenate]] ({{chem2|[PPh4]+[ReO4]−}})<ref>{{cite book |doi=10.1002/9780470132623.ch42|chapter=Tetrahalo Oxorhenate Anions|year=1996|last1=Dilworth|first1=J. R.|last2=Hussain|first2=W.|last3=Hutson|first3=A. J.|last4=Jones|first4=C. J.|last5=McQuillan|first5=F. S.|title=Inorganic Syntheses|pages=257–262|volume=XXXI|isbn=9780470132623}}</ref> and various [[thiomolybdate]]s.<ref>{{cite book |doi=10.1002/9780470132586.ch8|title=Tetraphenylphosphonium Salts of &#91;Mo₂(S)_n(S₂)_6-n]^2- Thioanions and Derivatives|series=Inorganic Syntheses|year=1990|last1=Hadjikyriacou|first1=A. I.|last2=Coucouvanis|first2=D.|chapter=Tetraphenylphosphonium Salts of &#91;Mo2 (S) N (S2 )6-N &#93;2- Thioanions and Derivatives|pages=39–47volume=XXVII|isbn=9780470132586}}</ref> Complexes of [[maleonitriledithiolate]] are also isolated as their {{chem2|[PPh4]+}} salts.<ref>{{cite book |doi=10.1002/9780470132449.ch39|title=Bis&#91;''cis''-1,2-Dicyanoethene-1,2-dithiolato(1- or 2-)&#93; Complexes of Cobalt and Iron|series=Inorganic Syntheses|year=1972|last1=Bray|first1=J.|last2=Locke|first2=J.|last3=McCleverty|first3=J. A.|last4=Coucouvanis|first4=D.|chapter=Bis&#91;cis -1,2-dicyanoethene-1,2-dithiolato(1- or 2-)&#93; Complexes of Cobalt and Iron|volume=XIII|pages=187–195|isbn=9780470132449}}</ref>

==References==

{{reflist}}

[[Category:Chlorides]]

[[Category:Quaternary phosphonium compounds]]

[[Category:Phenyl compounds]]

[[Category:Organophosphorus compounds]]