Manganese(III) chloride

Last updated
Manganese(III) chloride
Names
Other names
  • Manganese trichloride
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/3ClH.Mn/h3*1H;/q;;;+3/p-3
    Key: UDBAOKKMUMKEGZ-UHFFFAOYSA-K
  • Cl[Mn](Cl)Cl
Properties
MnCl3
Molar mass 161.30 g/mol
Melting point −18 °C (0 °F; 255 K)
Related compounds
Related compounds
 Manganese(II) chloride, Manganese(III) fluoride, Bis(triphenylphosphineoxide) manganese(III) chloride, Manganese(III) acetate, Manganese(III) acetylacetonate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Manganese(III) chloride is the hypothetical inorganic compound with the formula MnCl3.

Contents

The existence of this binary halide has not been demonstrated. [1] [2] Nonetheless, many derivatives of MnCl3 are known, such as MnCl3(THF)3 and the bench-stable MnCl3(OPPh3)2. Contrasting with the elusive nature of MnCl3, trichlorides of the adjacent metals on the periodic table—iron(III) chloride, chromium(III) chloride, and technetium(III) chloride—are all isolable compounds.

History of MnCl3 and its adducts

MnCl3 was claimed to be a dark solid and produced by the reaction of "anhydrous manganese(III) acetate" and liquid hydrogen chloride at −100 °C and decomposes above -40 °C. [3] Other claims involved reaction of manganese(III) oxide, manganese(III) oxide-hydroxide, and basic manganese acetate with hydrochloric acid. Given recent investigations however, such claims have been disproved or called into serious doubt. [4] Specifically, all known compounds containing MnCl3 are known to be solvent or ligand-stabilized adducts.

Adducts

MnCl3(OPPh3)2, a stable derivative form of MnCl3 Trichloridobistriphenylphosphineoxidemanganese(III).jpg
MnCl3(OPPh3)2, a stable derivative form of MnCl3

MnCl3 can be stabilized by complexation to diverse Lewis bases, as has been established over the course of many years of study. [4] Meta stable acetonitrile-solvated Mn(III)Cl3 can be prepared at room temperature by treating [Mn12O12(OAc)16(H2O)4] with trimethylsilyl chloride. [5] The treatment of permanganate salts with trimethylsilylchloride generates solutions containing Mn(III)–Cl species for alkene dichlorination reactions; [6] [7] [8] electrocatalytic methods that use Mn(III)–Cl intermediates have been developed for the same purpose. [9] [10]

The reaction of manganese dioxide with hydrochloric acid in tetrahydrofuran gives MnCl3(H2O)(THF)2. [4] Manganese(III) fluoride suspended in THF reacts with boron trichloride, giving MnCl3(THF)3 which has the appearance of dark purple prisms. [4] This compound has a monoclinic crystal structure, reacts with water, and decomposes at room temperature. [4]

The most readily handled of this series of adducts is MnCl3(OPPh3)2. [11]

Pentachloromanganate(III)

Another common manganese(III) chloride compound is the pentachloromanganate(III) dianion. It is usually charge balanced with counterion(s) like tetraethylammonium. [12] The pentachloromanganates are typically green in color, light sensitive, maintain pentacoordination in solution, and have S = 2 ground states at room temperature. [12] [13] Crystal structures of pentachloromanganate indicate the anion is square pyramidal. [14] [15] Tetraethylammonium pentachloromanganate(III), [Et4N]2[MnCl5], can be prepared and isolated by treating suspension of [Mn12O12(OAc)16(H2O)4] in diethyl ether with trimethylsilylchloride, collecting the resulting purple solid in the dark, and then treating this solid with 0.6 M solution of tetraethylammonium chloride. [5] The green product is air stable but should be kept in the dark.

Manganese(III) monochloride compounds

Some manganese compounds with macrocyclic tetradentate coordination can stabilize the manganese(III) monochloride, Mn(III)–Cl, moiety. Jacobson's catalyst is an example of a coordination compound containing the Mn(III)–Cl moiety and is stabilized by N,N,O,O coordination from a salen ligand. Jacobson's catalyst and related Mn(III)–Cl complexes react with O-atom transfer reagents to form high-valent Mn(V)O that are reactive in alkene epoxidation. Tetraphenylporphyrin Mn(III)Cl is a related commercially available compound.

Other manganese(III) chloride complexes

References

  1. ↑ Wiberg, Egon; Holleman, A. F.; Wiberg, Nils (2001). Inorganic chemistry. Nils Wiberg, A. F. Holleman (1st English ed.). San Diego: Academic Press. p. 1411. ISBN   0-12-352651-5. OCLC   48056955.
  2. ↑ Barber, M.; Linnett, J. W.; Taylor, N. H. (1961). "650. The halides of the transition elements of the first long period" . Journal of the Chemical Society (Resumed): 3323–3332. doi:10.1039/jr9610003323. ISSN   0368-1769.
  3. ↑ A. Chretien; G. Varga (1936). "Le chlorure de manganèse trivalent". Bulletin de la Société Chimique de France (in French) (3): 2385–2394.
  4. 1 2 3 4 5 Nachtigall, Olaf; Pataki, Astrid; Molski, Matthias; Lentz, Dieter; Spandl, Johann (May 2015). "Solvates of Manganese Trichloride Revisited - Synthesis, Isolation, and Crystal Structure of MnCl3(THF)3: Solvates of Manganese Trichloride Revisited" . Zeitschrift für anorganische und allgemeine Chemie. 641 (6): 1164–1168. doi:10.1002/zaac.201500106.
  5. 1 2 Perlepes, Spiros P.; Blackman, Allan G.; Huffman, John C.; Christou, George (April 1991). "Complete carboxylate removal from [Mn12O12(OAc)16(H2O)4].cntdot.2HOAc.cntdot.4H2O) with chlorotrimethylsilane: synthesis and characterization of polymeric (2,2'-bipyridine)trichloromanganese and an improved synthesis of bis(tetraethylammonium) pentachloromanganate(2-)" . Inorganic Chemistry. 30 (7): 1665–1668. doi:10.1021/ic00007a046. ISSN   0020-1669.
  6. ↑ Donnelly, K. D.; Fristad, W. E.; Gellerman, B. J.; Peterson, J. R.; Selle, B. J. (1984-01-01). "Chlorination of alkenes by manganese(III) chloride species" . Tetrahedron Letters. 25 (6): 607–610. doi:10.1016/S0040-4039(00)99950-7. ISSN   0040-4039.
  7. ↑ Bellesia, Franco; et al. (1989). "Chlorination of Alkenes with Manganese Dioxide-Trimethylchlorosilane" . Journal of the Chemical Society, Dalton Transactions (4): 108–109. doi:10.1039/DT98900BX019.
  8. ↑ Parisotto, Stefano; Azzi, Emanuele; Lanfranco, Alberto; Renzi, Polyssena; Deagostino, Annamaria (June 2022). "Recent Progresses in the Preparation of Chlorinated Molecules: Electrocatalysis and Photoredox Catalysis in the Spotlight". Reactions. 3 (2): 233–253. doi: 10.3390/reactions3020018 . hdl: 2318/1852481 . ISSN   2624-781X.
  9. ↑ Fu, Niankai; Sauer, Gregory S.; Lin, Song (2017-10-23). "Electrocatalytic Radical Dichlorination of Alkenes with Nucleophilic Chlorine Sources" . Journal of the American Chemical Society. 139 (43): 15548–15553. doi:10.1021/jacs.7b09388. ISSN   0002-7863. PMID   28988482.
  10. ↑ Dong, Xichang; Roeckl, Johannes L.; Waldvogel, Siegfried R.; Morandi, Bill (2021-01-29). "Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations". Science. 371 (6528): 507–514. Bibcode:2021Sci...371..507D. doi:10.1126/science.abf2974. hdl: 20.500.11850/466816 . ISSN   0036-8075. PMID   33510026. S2CID   231731258.
  11. ↑ Saju, Ananya; Griffiths, Justin R.; MacMillan, Samantha N.; Lacy, David C. (2022-09-06). "Synthesis of a Bench-Stable Manganese(III) Chloride Compound: Coordination Chemistry and Alkene Dichlorination". Journal of the American Chemical Society. 144 (37): 16761–16766. doi:10.1021/jacs.2c08509. ISSN   0002-7863. PMC   11648269 . PMID   36067378. S2CID   252110339.
  12. 1 2 Levason, W.; McAuliffe, C. A. (1973-01-01). "The co-ordination chemistry of manganese. Part II. Some pentachloromanganates(III)" . Journal of the Chemical Society, Dalton Transactions (4): 455–458. doi:10.1039/DT9730000455. ISSN   1364-5447.
  13. ↑ Akabori, Kozo (1974-12-05). "Thermal properties of n, n′-dihydro-1,10-phenanthrolinium and n,n′-dihydro-2, 2′-bipyridinium pentachloromanganates(iii)" . Chemistry Letters. 3 (12): 1481–1486. doi:10.1246/cl.1974.1481. ISSN   0366-7022.
  14. ↑ Bernal, Ivan; Elliott, Norman; Lalancette, Roger (1971-01-01). "Molecular configuration of the anion MnCl52–—a square pyramidal pentahalide of the 3d transition series" . Journal of the Chemical Society D: Chemical Communications (15): 803–804. doi:10.1039/C29710000803. ISSN   0577-6171.
  15. ↑ Matsui, Masanori; Koda, Shigetaka; Ooi, Shun′ichiro; Kuroya, Hisao; Bernal, Ivan (1972-01-05). "THE CRYSTAL STRUCTURE OF PHENANTHROLINIUM PENTACHLOROMANGANATE(III), (phenH2)(MnCl5)". Chemistry Letters. 1 (1): 51–53. doi:10.1246/cl.1972.51. ISSN   0366-7022.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.