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{{chembox |
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| verifiedrevid = 409169692 |
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| verifiedrevid = 447561260 |
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| ImageFile = PPNCl.png |
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| Name = |
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| ImageFile = PPNCl.png |
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| IUPACName = μ-nitrido-Bis(triphenylphosphorus) chloride |
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| PIN = Hexaphenyl-1λ<sup>5</sup>-diphosphaz-1-en-3-ium chloride |
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| OtherNames = PPN chloride<br />Bis(triphenylphosphine)iminium chloride<br />Bis(triphenylphosphoranylidene)iminium chloride<br />Bis(triphenylphosphoranylidene)ammonium chloride<br />Hexaphenyldiphosphazenium chloride<br />Selectophore |
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| OtherNames = PNP chloride <br /> |
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PPN chloride<br />Bis(triphenylphosphine)iminium chloride<br />Bis(triphenylphosphoranylidene)iminium chloride<br />Bis(triphenylphosphoranylidene)ammonium chloride<br />Hexaphenyldiphosphazenium chloride<br />Selectophore |
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| SystematicName = |
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| Section1 = {{Chembox Identifiers |
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| Section1 = {{Chembox Identifiers |
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| SMILES = .N((c1ccccc1)(c2ccccc2)c3ccccc3)=P(c4ccccc4)(c5ccccc5)c6ccccc6 |
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| SMILES = .N((c1ccccc1)(c2ccccc2)c3ccccc3)=P(c4ccccc4)(c5ccccc5)c6ccccc6 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 2300634 |
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| ChemSpiderID = 2300634 |
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| PubChem = 3036656 |
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| PubChem = 3036656 |
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| EC_number = 244-170-6 |
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| InChI = 1/C36H30NP2.ClH/c1-7-19-31(20-8-1)38(32-21-9-2-10-22-32,33-23-11-3-12-24-33)37-39(34-25-13-4-14-26-34,35-27-15-5-16-28-35)36-29-17-6-18-30-36;/h1-30H;1H/q+1;/p-1 |
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| InChI = 1/C36H30NP2.ClH/c1-7-19-31(20-8-1)38(32-21-9-2-10-22-32,33-23-11-3-12-24-33)37-39(34-25-13-4-14-26-34,35-27-15-5-16-28-35)36-29-17-6-18-30-36;/h1-30H;1H/q+1;/p-1 |
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| InChIKey = LVRCYPYRKNAAMX-REWHXWOFAO |
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| InChIKey = LVRCYPYRKNAAMX-REWHXWOFAO |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = LVRCYPYRKNAAMX-UHFFFAOYSA-M |
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| StdInChIKey = LVRCYPYRKNAAMX-UHFFFAOYSA-M |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = 21050-13-5 |
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| CASNo = 21050-13-5 |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| Formula = C<sub>36</sub>H<sub>30</sub>ClNP<sub>2</sub> |
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| Formula = {{chem2|Cl}} |
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| MolarMass = 574.03 g/mol |
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| MolarMass = 574.03 g/mol |
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| Appearance = colourless solid |
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| Appearance = colourless solid |
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| Solubility = moderate |
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| Density = ?? g/cm<sup>3</sup>, solid |
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| MeltingPtC = 260 to 262 |
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| Solubility = moderate |
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| MeltingPt = 260-2 °C |
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| Section3 = |
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| Section7 = {{Chembox Hazards |
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| Section7 = {{Chembox Hazards |
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| GHSPictograms = {{GHS07}} |
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| RPhrases = 36/37/38 |
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| GHSSignalWord = Warning |
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| SPhrases = 26-36 |
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| HPhrases = {{H-phrases|315|319|332|335}} |
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| PPhrases = {{P-phrases|261|264|271|280|302+352|304+312|304+340|305+351+338|312|321|332+313|337+313|362|403+233|405|501}} |
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| Section8 = {{Chembox Other |
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| Section8 = {{Chembox Related |
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| OtherCpds = Tetraphenylarsonium chloride<br />Tetrabutylammonium chloride<br />tetrabutylammonium chloride}} |
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| OtherCompounds = ]<br />]}} |
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'''Bis(triphenylphosphine)iminium chloride''' is the ] with the formula Cl, often written Cl and abbreviated PPNCl. This ]less salt is a source of the PPN<sup>+</sup> cation, which is used to isolate reactive anions. PPN<sup>+</sup> is a ]. |
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'''Bis(triphenylphosphine)iminium chloride''' is the ] with the formula {{chem2|Cl}}, often abbreviated {{chem2|Cl}}, where Ph is ] {{chem2|C6H5}}, or even abbreviated Cl or Cl or PPNCl or PNPCl, where PPN or PNP stands for {{chem2|(Ph3P)2N}}. This ]less salt is a source of the {{chem2|+}} cation (abbreviated {{chem2|PPN+}} or {{chem2|PNP+}}), which is used as an unreactive and weakly coordinating cation to isolate reactive anions. {{chem2|+}} is a ]. |
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==Synthesis and structure== |
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==Synthesis and structure== |
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PPNCl is prepared in two steps from ]:<ref>{{cite journal | author = J. K. Ruff; W. J. Schlientz; R. E. Dessy; J. M. Malm; G. R. Dobson; M. N. Memering | title = μ-nitrido-Bis(triphenylphosphorus)(1+ (“PPN”) Salts with Metal Carbonyl Anions | journal = ] | volume = 15 | year = 1974 | pages = 84–90 | doi = 10.1002/9780470132463.ch19}}</ref> |
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{{chem2|Cl}} is prepared in two steps from ] {{chem2|Ph3P}}:<ref name=Ruff>{{cite book | last1 = Ruff|first1=J.K.|last2=Schlientz|first2=W.J. |title=Inorganic Syntheses |chapter=μ-Nitridobis(triphenylphosphorus)(l+) ("PPN") Salts with Metal Carbonyl Anions | journal = ] | volume = 15 | year = 1974 | pages = 84–90 | doi = 10.1002/9780470132463.ch19|isbn=9780470132463}}</ref> |
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:{{chem2|Ph3P + Cl2 → Ph3PCl2}} |
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:Ph<sub>3</sub>P + Cl<sub>2</sub> → Ph<sub>3</sub>PCl<sub>2</sub> |
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This ] is related to ]. Treatment of this species with ] in the presence of Ph<sub>3</sub>P results in replacement of the P-Cl bonds by P=N bonds: |
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This ] {{chem2|Ph3PCl2}} is related to ] {{chem2|PCl5}}. Treatment of this species with ] in the presence of {{chem2|Ph3P}} results in replacement of the two single P–Cl bonds in {{chem2|Ph3PCl2}} by one double P=N bond: |
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:{{chem2|2 Ph3PCl2 + NH2OH*HCl + Ph3P → Cl + 4HCl + Ph3PO}} |
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:2 Ph<sub>3</sub>PCl<sub>2</sub> + NH<sub>2</sub>OH·HCl + Ph<sub>3</sub>P → {<sub>2</sub>N}Cl + 4HCl + ] |
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] {{chem2|Ph3PO}} is a by-product. |
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Bis(triphenylphosphine)iminium chloride is described as {{chem2|+Cl-}}. The structure of the bis(triphenylphosphine)iminium cation {{chem2|+}} is {{chem2|+}}. The P=N=P angle in the cation is flexible, ranging from ~130 to 180° depending on the salt. Bent and linear forms of the P=N=P connections have been observed in the same unit cell.<ref>{{cite journal|last1=Hardy|first1=Gordon E.|last2=Zink|first2=Jeffrey I.|last3=Kaska|first3=W. C.|last4=Baldwin|first4=J. C. | name-list-style = vanc |date= December 1978|title=Structure and triboluminescence of polymorphs of hexaphenylcarbodiphosphorane |journal=Journal of the American Chemical Society |volume=100|issue=25|pages=8001–8002|doi=10.1021/ja00493a035 }}</ref> The same shallow potential well for bending is observed in the isoelectronic species ], {{chem2|Ph3P\dC\dPPH3}}, as well as the more distantly related molecule ], {{chem2|O\dC\dC\dC\dO}}. For the solvent-free chloride salt {{chem2|Cl}}, the P=N=P bond angle was determined to be 133°.<ref>{{cite journal | vauthors = Knapp C, Uzun R | title = Solvate-free bis-(triphenylphosphine)iminium chloride | journal = Acta Crystallographica Section E | volume = 66 | issue = Pt 12 | pages = o3185 | date = November 2010 | pmid = 21589480 | pmc = 3011587 | doi = 10.1107/S1600536810046325 }}</ref> The two P=N bonds are equivalent, and their length is 1.597(2) Å. |
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In PPN<sup>+</sup> salts, P-N bond lengths are equivalent, 1.58 Å. The cation has idealized centrosymmetry (D<sub>3d</sub> point group), although in the solid state, deviations from this high symmetry are often observed. Its connectivity is indicated by Ph<sub>3</sub>P=N=PPh<sub>3</sub><sup>+</sup>. |
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<center>]</center> |
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==Applications== |
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==Use as reagent== |
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In the laboratory, PPN chloride is the main precursor to PPN<sup>+</sup> salts. Using salt metathesis reactions, ], ], and other small inorganic anions can be obtained with PPN<sup>+</sup> cations. The resulting salts PPNNO<sub>2</sub>, PPNN<sub>3</sub> etc are soluble in polar organic solvents. |
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In the laboratory, {{chem2|Cl}} is the main precursor to {{chem2|+}} salts. Using salt metathesis reactions, ], ], and other small inorganic anions can be obtained with {{chem2|+}} cations. The resulting salts {{chem2|+NO2-}}, {{chem2|+N3-}}, etc. are soluble in polar organic solvents. |
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PPN<sup>+</sup> forms crystalline salts with a range of anions that are otherwise difficult to crystallize. Its effectiveness is partially attributable to its rigidity, reflecting the presence of six phenyl rings. Often PPN<sup>+</sup> forms salts that are more air-stable than salts with smaller cations such as those containing ] or alkali metal cations. This effect is attributed to the steric shielding provided by this voluminous cation. Illustrative PPN<sup>+</sup> salts of reactive anions include PPN, PPN, and PPN. The role of ]ing in chemical reactions is often clarified by examination of the related salt derived from PPN<sup>+</sup>. |
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{{chem2|+}} forms crystalline salts with a range of anions that are otherwise difficult to crystallize. Its effectiveness is partially attributable to its rigidity, reflecting the presence of six phenyl rings. Often {{chem2|+}} forms salts that are more air-stable than salts with smaller cations such as those containing ] cation {{chem2|+}}, or ] cations. This effect is attributed to the steric shielding provided by this voluminous cation. Illustrative {{chem2|+}} salts of reactive anions include {{chem2|+-}}, {{chem2|+-}}, {{chem2|(+)2(2+)}} (M = Cr, Mo, W), and {{chem2|+-}}.<ref name=Ruff/> The role of ]ing in chemical reactions is often clarified by examination of the related salt derived from {{chem2|+}}. |
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==References== |
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==Related cations== |
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A phosphazenium cation related to {{chem2|+}} is {{chem2|+}}.<ref>{{cite encyclopedia|author=Schwesinger, Reinhard|title=1,1,1,3,3,3-Hexakis(dimethylamino)-1λ5,3λ5-diphosphazenium fluoride|encyclopedia=e-EROS Encyclopedia of Reagents for Organic Synthesis|year=2001|pages=1–2|doi=10.1002/047084289X.rh014m|isbn=0471936235}}</ref> |
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== References == |
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