Triethylmethylammonium trichloride

Triethylmethylammonium trichloride
Identifiers
CAS Number	2460902-02-5;
3D model (JSmol)	Interactive image;
PubChem CID	162420758;
	InChI InChI=1S/C7H18N.Cl3/c1-5-8(4,6-2)7-3;1-3-2/h5-7H2,1-4H3;/q+1;-1 Key: BZFQYOSNSCXXBQ-UHFFFAOYSA-N;
	SMILES CC[N+](CC)(CC)C.Cl[Cl-]Cl;
Properties
Chemical formula	C7H18Cl3N
Molar mass	222.58 g·mol−1
Appearance	yellow liquid
Related compounds
Related compounds	Tetraethylammonium trichloride
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Triethylmethylammonium trichloride [NEt3Me][Cl3] is an ionic liquid consisting of an asymmetric triethylmethylammonium cation and a trichloride anion. The trichloride is also known as trichlorine monoanion representing one of the simplest polychlorine anions.^[1]

Preparation[edit]

Triethylmethylammonium trichloride is prepared by the reaction of triethylmethylammonium chloride and elemental chlorine gas.^[2]

[NEt₃Me]Cl + Cl₂ → [NEt₃Me][Cl₃]

Structure and chemical bonding[edit]

According to the halogen bonding concept, the trichloride anion can be described as a donor-acceptor complex consisting of a chloride anion (the halogen donor) and a dichlorine molecule (the halogen acceptor). By donation of electron density of the chloride anion into the σ-hole of the dichlorine molecule lying along the Cl-Cl bonding axis. In this way, the trichloride anion ([Cl-Cl-Cl]⁻) is formed which theoretically adopts a linear geometry with Cl-Cl bonds of equal length.^[3] However, the real structure of the trichloride anion is typically slightly different due to interaction of the trichloride anion with cations or anisotropic effects in the solid state.^[1]

A more precise definition of triethylmethylammonium trichloride is given by the sum formula [NEt₃Me][Cl(Cl₂)_n] where n is the number of equivalents of dichlorine that are bonded. By addition of elemental chlorine to [NEt₃Me]Cl (n = 0), the value of n increases continuously forming the trichloride [NEt₃Me][Cl₃] (n = 1), the pentachloride [NEt₃Me][Cl₅] (n = 2) and, at higher chlorine loadings, higher polychlorides. For values of n < 0.8, [NEt₃Me][Cl(Cl₂)_n] is a yellow solid, while for n > 0.8 [NEt₃Me][Cl(Cl₂)_n] exists as an ionic liquid at room temperature.^[1]^[2]

Applications[edit]

Triethylmethylammonium trichloride [NEt3Me][Cl3] shows a similar reactivity like tetraethylammonium trichloride or elemental chlorine but is easier to handle than chlorine gas as it is a liquid at room temperature. For instance, alkenes are chlorinated with triethylmethylammonium trichloride providing the corresponding vicinal 1,2-dichloroalkanes.^[2] Recently, the reaction of triethylmethylammonium trichloride with carbon monoxide to form phosgene was described. In this reaction, carbon monoxide is oxidized at room temperature. Alternatively, the reaction can be performed utilizing catalytical amounts of [NEt₃Me]Cl in the presence of elemental chlorine forming presumably the catalytically active species [NEt₃Me][Cl₃] which reacts with carbon monoxide yielding phosgene and forming [NEt₃Me]Cl.^[2]

[NEt₃Me][Cl₃] + CO → COCl₂ + [NEt₃Me]Cl

References[edit]

^ ^a ^b ^c Karsten Sonnenberg, Lisa Mann, Frenio A. Redeker, Benjamin Schmidt, Sebastian Riedel (2020), "Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine", Angewandte Chemie International Edition (in German), vol. 59, no. 14, pp. 5464–5493, doi:10.1002/anie.201903197, ISSN 1521-3773, PMID 31090163, S2CID 155093006, retrieved 2022-02-01{{citation}}: CS1 maint: multiple names: authors list (link)
^ ^a ^b ^c ^d Patrick Voßnacker, Alisa Wüst, Thomas Keilhack, Carsten Müller, Simon Steinhauer (October 2021), "Novel synthetic pathway for the production of phosgene", Science Advances (in German), vol. 7, no. 40, pp. eabj5186, Bibcode:2021SciA....7.5186V, doi:10.1126/sciadv.abj5186, ISSN 2375-2548, PMC 8480918, PMID 34586844{{citation}}: CS1 maint: multiple names: authors list (link)
^ Keil, Helena; Sonnenberg, Karsten; Müller, Carsten; Herbst-Irmer, Regine; Beckers, Helmut; Riedel, Sebastian; Stalke, Dietmar (February 2021). "Insights into the Topology and the Formation of a Genuine ppσ Bond: Experimental and Computed Electron Densities in Monoanionic Trichlorine [Cl₃]⁻". Angewandte Chemie International Edition. 60 (5): 2569–2573. doi:10.1002/anie.202013727. ISSN 1433-7851. PMC 7898528. PMID 33151006.

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[:1-1] Karsten Sonnenberg, Lisa Mann, Frenio A. Redeker, Benjamin Schmidt, Sebastian Riedel (2020), "Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine", Angewandte Chemie International Edition (in German), vol. 59, no. 14, pp. 5464–5493, doi:10.1002/anie.201903197, ISSN 1521-3773, PMID 31090163, S2CID 155093006, retrieved 2022-02-01{{citation}}: CS1 maint: multiple names: authors list (link)

[:0-2] Patrick Voßnacker, Alisa Wüst, Thomas Keilhack, Carsten Müller, Simon Steinhauer (October 2021), "Novel synthetic pathway for the production of phosgene", Science Advances (in German), vol. 7, no. 40, pp. eabj5186, Bibcode:2021SciA....7.5186V, doi:10.1126/sciadv.abj5186, ISSN 2375-2548, PMC 8480918, PMID 34586844{{citation}}: CS1 maint: multiple names: authors list (link)

[3] Keil, Helena; Sonnenberg, Karsten; Müller, Carsten; Herbst-Irmer, Regine; Beckers, Helmut; Riedel, Sebastian; Stalke, Dietmar (February 2021). "Insights into the Topology and the Formation of a Genuine ppσ Bond: Experimental and Computed Electron Densities in Monoanionic Trichlorine [Cl₃]⁻". Angewandte Chemie International Edition. 60 (5): 2569–2573. doi:10.1002/anie.202013727. ISSN 1433-7851. PMC 7898528. PMID 33151006.

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