Misplaced Pages

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

The existence of this binary halide has not been demonstrated. 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. 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. Specifically, all known compounds containing MnCl₃ are known to be solvent or ligand-stabilized adducts.

Adducts

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

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

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

Pentachloromanganate(III)

Another common manganese(III) chloride compound is the pentachloromanganate(III) dianion. It is usually charge balanced with counterion(s) like tetraethylammonium. The pentachloromanganates are typically green in color, light sensitive, maintain pentacoordination in solution, and have S = 2 ground states at room temperature. Crystal structures of pentachloromanganate indicate the anion is square pyramidal. Tetraethylammonium pentachloromanganate(III), ₂, can be prepared and isolated by treating suspension of 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. 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

• Bis(triphenylphosphineoxide) manganese(III) chloride

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. ^ 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. ^ 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. ^ 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.

• Manganese(III) compounds
• Chlorides