µ-nitrido-bis (triphenylphosphine) chloride

Structural formula
General
Surname	µ-nitrido-bis (triphenylphosphine) chloride
other names	PPNCl; Triphenyl ( P , P , P -triphenylphosphinimidato) phosphorus (1+) chloride; Bis (triphenylphosphine) iminium chloride; Bis (triphenylphosphoranylidene) iminium chloride; Bis (triphenylphosphoranylidene) ammonium chloride; Hexaphenyl diphosphazene chloride;
Molecular formula	C 36 H 30 ClNP 2
Brief description	beige powder
External identifiers / databases
EC number	244-170-6
ECHA InfoCard	100.040.139
PubChem	3036656
Wikidata	Q172272
properties
Molar mass	574.03 g · mol -1
Physical state	firmly
Melting point	273-274 ° C
safety instructions
GHS labeling of hazardous substances Caution
H and P phrases	H: 315-319-332-335
	P: 261-305 + 351 + 338
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

µ-Nitrido-bis (triphenylphosphine) chloride is a chemical substance with the empirical formula [((C ₆ H ₅ ) ₃ P) ₂ N] Cl, which is often abbreviated as PPNCl. The colorless salt is a source of [PPN] ⁺ - cation to otherwise difficult, which is used anions crystallize. [PPN] ⁺ is a phosphazene .

Manufacturing

The representation of PPNCl takes place in two steps from triphenylphosphane :

{\ displaystyle \ mathrm {Ph_ {3} P \ + \ Cl_ {2} \ rightarrow \ Ph_ {3} PCl_ {2}}}

The resulting triphenylphosphine dichloride is a chlorination reaction used in organic chemistry , which is present as an ion pair in polar solvents and as a trigonal bipyramidal molecule in non-polar solvents . Further treatment with hydroxylamine in the presence of an equivalent of Ph ₃ P results in the replacement of the P-Cl bonds with P = N bonds:

{\ displaystyle \ mathrm {2 \ Ph_ {3} PCl_ {2} \ + \ NH_ {2} OH \ cdot HCl \ + \ Ph_ {3} P}}

{\ displaystyle \ mathrm {\ rightarrow [(Ph_ {3} P) _ {2} N] Cl \ + \ 4 \ HCl \ + \ Ph_ {3} PO}}

application

PPN chloride is the most important precursor for other [PPN] ⁺ salts. Nitrites , azides and other small inorganic anions with [PPN] ⁺ as a cation can be obtained by displacement reactions . These salts are soluble in polar organic solvents. [PPN] ⁺ salts enable the crystallization of compounds with anions whose metal salts would be unstable in the solid phase .

Individual evidence

↑ ^a ^b ^c data sheet bis (triphenylphosphoranylidene) ammonium chloride from Sigma-Aldrich , accessed on October 18, 2016 ( PDF ).
↑ ^a ^b A. Martinsen, J. Songstad: Preparation and Properties of Some Bis (triphenylphosphine) -iminium Salts, [(Ph ₃ P) ₂ N] X . In: Acta Chemica Scandinavica . A31, 1977, p. 645-650 .
↑ JK Ruff, WJ Schlientz: μ-nitrido-Bis (triphenylphosphorus) (1+) (“PPN”) Salts with Metal Carbonyl Anions . In: Inorganic Syntheses . tape XV , 1974, p. 84-90 .
↑ e-EROS Encyclopedia of Reagents for Organic Synthesis, doi : 10.1002 / 047084289X.rt371
↑ SM Godfrey, CA McAuliffe, RG Pritchard, JM Sheffield: An X-ray crystallorgraphic study of the reagent Ph ₃ PCl ₂ ; not charge-transfer, R ₃ P – Cl – Cl, trigonal bipyramidal or [R ₃ PCl] Cl but an unusual dinuclear ionic species, [Ph ₃ PCl ⁺ ... Cl ^- ... ⁺ CIPPH ₃ ] Cl containing long Cl –Cl contacts . In: Chemical Communications . 1996, p. 2521-2522 , doi : 10.1039 / CC9960002521 .
↑ SM Godfrey, CA McAuliffe, JM Sheffield: Structural dependence of the reagent Ph ₃ PCl ₂ on the nature of the solvent, both in the solid state and in solution; X-ray crystal structure of trigonal bipyramidal Ph ₃ PCl ₂ , the first structurally characterized five-coordinate R ₃ PCl ₂ compound. In: Chemical Communications . 1998, p. 921-922 , doi : 10.1039 / a800820e .
^ JK Ruff: Chemistry of the dinuclear carbonyl anions. II. Mixed-metal derivatives . In: Inorganic Chemistry . tape 7 , 1968, p. 1818-1821 , doi : 10.1021 / ic50067a023 .
↑ LB Handy, JK Ruff, LF Dahl: Structural characterization of the dinuclear metal carbonyl anions [M ₂ (CO) ₁₀ ] ^{2 -} (M = chromium, molybdenum) and [Cr ₂ (CO) ₁₀ H] ^- . Marked stereochemical effect of a linearly protonated metal-metal bond. In: Inorganic Chemistry . tape 92 , 1970, pp. 7312-7326 , doi : 10.1021 / ja00728a014 .

[Sigma-1] ta sheet bis (triphenylphosphoranylidene) ammonium chloride from Sigma-Aldrich , accessed on October 18, 2016 ( PDF ).

[martinsen-2] A. Martinsen, J. Songstad: Preparation and Properties of Some Bis (triphenylphosphine) -iminium Salts, [(Ph ₃ P) ₂ N] X . In: Acta Chemica Scandinavica . A31, 1977, p. 645-650 .

[ruff-schlientz-3] JK Ruff, WJ Schlientz: μ-nitrido-Bis (triphenylphosphorus) (1+) (“PPN”) Salts with Metal Carbonyl Anions . In: Inorganic Syntheses . tape XV , 1974, p. 84-90 .

[e-EROS-4] -EROS Encyclopedia of Reagents for Organic Synthesis, doi : 10.1002 / 047084289X.rt371

[Godfrey_1996-5] SM Godfrey, CA McAuliffe, RG Pritchard, JM Sheffield: An X-ray crystallorgraphic study of the reagent Ph ₃ PCl ₂ ; not charge-transfer, R ₃ P – Cl – Cl, trigonal bipyramidal or [R ₃ PCl] Cl but an unusual dinuclear ionic species, [Ph ₃ PCl ⁺ ... Cl ^- ... ⁺ CIPPH ₃ ] Cl containing long Cl –Cl contacts . In: Chemical Communications . 1996, p. 2521-2522 , doi : 10.1039 / CC9960002521 .

[Godfrey_1998-6] SM Godfrey, CA McAuliffe, JM Sheffield: Structural dependence of the reagent Ph ₃ PCl ₂ on the nature of the solvent, both in the solid state and in solution; X-ray crystal structure of trigonal bipyramidal Ph ₃ PCl ₂ , the first structurally characterized five-coordinate R ₃ PCl ₂ compound. In: Chemical Communications . 1998, p. 921-922 , doi : 10.1039 / a800820e .

[ruff-7] JK Ruff: Chemistry of the dinuclear carbonyl anions. II. Mixed-metal derivatives . In: Inorganic Chemistry . tape 7 , 1968, p. 1818-1821 , doi : 10.1021 / ic50067a023 .

[handy-8] LB Handy, JK Ruff, LF Dahl: Structural characterization of the dinuclear metal carbonyl anions [M ₂ (CO) ₁₀ ] ^{2 -} (M = chromium, molybdenum) and [Cr ₂ (CO) ₁₀ H] ^- . Marked stereochemical effect of a linearly protonated metal-metal bond. In: Inorganic Chemistry . tape 92 , 1970, pp. 7312-7326 , doi : 10.1021 / ja00728a014 .