| 词条 | Bis(triphenylphosphine)iminium chloride |
| 释义 |
| Watchedfields = changed | verifiedrevid = 447561260 | ImageFile = PPNCl.png | ImageName = | IUPACName = μ-nitrido-Bis(triphenylphosphorus) chloride | OtherNames = PPN chloride Bis(triphenylphosphine)iminium chloride Bis(triphenylphosphoranylidene)iminium chloride Bis(triphenylphosphoranylidene)ammonium chloride Hexaphenyldiphosphazenium chloride Selectophore |Section1={{Chembox Identifiers | SMILES = [Cl-].N([P+](c1ccccc1)(c2ccccc2)c3ccccc3)=P(c4ccccc4)(c5ccccc5)c6ccccc6 | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID = 2300634 | PubChem = 3036656 | 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 | InChIKey = LVRCYPYRKNAAMX-REWHXWOFAO | StdInChI_Ref = {{stdinchicite|correct|chemspider}} | StdInChI = 1S/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 | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey = LVRCYPYRKNAAMX-UHFFFAOYSA-M | CASNo_Ref = {{cascite|correct|??}} | CASNo = 21050-13-5 |Section2={{Chembox Properties | Formula = C36H30ClNP2 | MolarMass = 574.03 g/mol | Appearance = colourless solid | Solubility = moderate | MeltingPtC = 260 to 262 | MeltingPt_notes = |Section7={{Chembox Hazards | RPhrases = 36/37/38 | SPhrases = 26–36 |Section8={{Chembox Related | OtherCompounds = Tetraphenylarsonium chloride Tetrabutylammonium chloride tetrabutylammonium chloride}} }} Bis(triphenylphosphine)iminium chloride is the chemical compound with the formula [(C6H5)3P)2N]Cl, often written [(Ph3P)2N]Cl and abbreviated PPNCl. This colorless salt is a source of the PPN+ cation, which is used to isolate reactive anions. PPN+ is a phosphazene. Synthesis and structurePPNCl is prepared in two steps from triphenylphosphine:[1] Ph3P + Cl2 → Ph3PCl2 This triphenylphosphine dichloride is related to phosphorus pentachloride. Treatment of this species with hydroxylamine in the presence of Ph3P results in replacement of the P-Cl bonds by P=N bonds: 2 Ph3PCl2 + NH2OH·HCl + Ph3P → {[Ph3P]2N}Cl + 4HCl + Ph3PO The PNP angle in the cation is flexible, ranging from ~130 to 180° depending on the salt. Bent and linear forms have been observed in the same unit cell.[2] The same shallow potential well for bending is observed in the isoelectronic species bis(triphenylphosphoranylidene)methane, (Ph3P)2C, as well as the more distantly related molecule carbon suboxide. For the solvent-free chloride salt, the PNP bond angle was determined to be 133°.[3] The P-N bond lengths are equivalent at 1.597(2) Å. ApplicationsIn the laboratory, PPN chloride is the main precursor to PPN+ salts. Using salt metathesis reactions, nitrite, azide, and other small inorganic anions can be obtained with PPN+ cations. The resulting salts PPNNO2, PPNN3 etc. are soluble in polar organic solvents. PPN+ 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+ forms salts that are more air-stable than salts with smaller cations such as those containing quaternary ammonium or alkali metal cations. This effect is attributed to the steric shielding provided by this voluminous cation. Illustrative PPN+ salts of reactive anions include PPN[HFe(CO)4], PPN[Co(CO)4], and PPN[Fe(CO)3NO]. The role of ion pairing in chemical reactions is often clarified by examination of the related salt derived from PPN+. Related cationsA phosphazenium cation related to PPN+ is {[(CH3)2N)3P]2N}+.[4] References1. ^{{cite journal | vauthors = Ruff JK, Schlientz WJ, Dessy RE, Malm JM, Dobson GR, Memering MN | title = μ-nitrido-Bis(triphenylphosphorus)(1+ ("PPN") Salts with Metal Carbonyl Anions | journal = Inorg. Synth. | volume = 15 | year = 1974 | pages = 84–90 | doi = 10.1002/9780470132463.ch19}} 2. ^{{cite journal|last=Hardy|first=Gordon E.|last2=Zink|first2=Jeffrey I.|last3=Kaska|first3=W. C.|last4=Baldwin|first4=J. C. | name-list-format = 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 }} 3. ^{{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 }} 4. ^{{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}} 2 : Organophosphorus compounds|Chlorides |
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