Manganese(III) chloride

Manganese(III) chloride  Names

Other names

* Manganese trichloride

Identifiers
ChemSpider |

* 8329698

PubChem CID

* 12029980

Properties

Chemical formula

| MnCl3
Molar mass | 161.30 g/mol
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).

Infobox references

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

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.

## Contents

* 1 History of MnCl3 and its adducts
* 1.1 Adducts
* 1.2 Pentachloromanganate(III)
* 2 Manganese(III) monochloride compounds
* 3 Other manganese(III) chloride complexes
* 4 References

## 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

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 change 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

* 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. pp. 1411. ISBN 0-12-352651-5. OCLC 48056955. https://www.worldcat.org/oclc/48056955.
2. ↑ Barber, M.; Linnett, J. W.; Taylor, N. H. (1961). "650. The halides of the transition elements of the first long period" (in en). Journal of the Chemical Society (Resumed): 3323–3332. doi:10.1039/jr9610003323. ISSN 0368-1769. http://xlink.rsc.org/?DOI=jr9610003323.
3. ↑ A. Chretien; G. Varga (1936). "Le chlorure de manganèse trivalent" (in French). Bulletin de la Société Chimique de France (3): 2385–2394. https://books.google.com/books?id=vR1HAQAAIAAJ.
4. ↑ 4.0 4.1 4.2 4.3 4.4 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" (in en). Zeitschrift für anorganische und allgemeine Chemie 641 (6): 1164–1168. doi:10.1002/zaac.201500106. https://onlinelibrary.wiley.com/doi/10.1002/zaac.201500106.
5. ↑ 5.0 5.1 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-)"] (in en). Inorganic Chemistry 30 (7): 1665–1668. doi:10.1021/ic00007a046. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic00007a046.
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" (in en). Tetrahedron Letters 25 (6): 607–610. doi:10.1016/S0040-4039(00)99950-7. ISSN 0040-4039. https://www.sciencedirect.com/science/article/pii/S0040403900999507.
7. ↑ Bellesia, Franco (1989). "Chlorination of Alkenes with Manganese Dioxide-Trimethylchlorosilane". Journal of the Chemical Society, Dalton Transactions (4): 108–109. doi:10.1039/DT98900BX019. https://pubs.rsc.org/en/Content/ArticlePDF/1989/DT/DT98900BX019?page=Search.
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" (in en). Reactions 3 (2): 233–253. doi:10.3390/reactions3020018. 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. http://dx.doi.org/10.1021/jacs.7b09388.
10. ↑ Dong, Xichang; Roeckl, Johannes L.; Waldvogel, Siegfried R.; Morandi, Bill (2021-01-29). "Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations" (in en). Science 371 (6528): 507–514. doi:10.1126/science.abf2974. ISSN 0036-8075. PMID 33510026. Bibcode: 2021Sci...371..507D. https://www.science.org/doi/10.1126/science.abf2974.
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" (in en). Journal of the American Chemical Society 144 (37): 16761–16766. doi:10.1021/jacs.2c08509. ISSN 0002-7863. PMID 36067378. https://pubs.acs.org/doi/10.1021/jacs.2c08509.
12. ↑ 12.0 12.1 Levason, W.; McAuliffe, C. A. (1973-01-01). "The co-ordination chemistry of manganese. Part II. Some pentachloromanganates(III)" (in en). Journal of the Chemical Society, Dalton Transactions (4): 455–458. doi:10.1039/DT9730000455. ISSN 1364-5447. https://pubs.rsc.org/en/content/articlelanding/1973/dt/dt9730000455.
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. https://www.journal.csj.jp/doi/10.1246/cl.1974.1481.
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" (in en). Journal of the Chemical Society D: Chemical Communications (15): 803–804. doi:10.1039/C29710000803. ISSN 0577-6171. https://pubs.rsc.org/en/content/articlelanding/1971/c2/c29710000803.
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.

* v
* t
* e

Manganese compounds

* MnO
* Mn3O4
* Mn5O8
* MnS
* MnS2
* MnSO4
* MnSe2
* MnSe
* MnTe
* Mn(NO3)2
* MnCO3
* MnCl2
* MnCl3
* MnCl4
* MnF2
* MnBr2
* MnI2
* MnTiO3
* MnMoO4
* Mn(CH3COO)2
* Mn2O3
* MnF3
* K6Mn2O6
* MnO2
* Mn(OH)2
* MnO3
* K3MnO4
* MnF4
* Na2MnO4
* K2MnO4
* Mn2O7
* NaMnO4
* KMnO4
* NH4MnO4
* AgMnO4
* Ca(MnO4)2
* Ba(MnO4)2
* MnH(CO)5
* Mn2(CO)10

* v
* t
* e

Salts and covalent derivatives of the chloride ion

HCl |  |  |  | He

|
|
|
|

LiCl | BeCl2 | BCl3
B2Cl4 | CCl4 | NCl3
ClN3 | Cl2O
ClO2
Cl2O7 | ClF
ClF3
ClF5 | Ne
NaCl | MgCl2 | AlCl
AlCl3 | SiCl4 | P2Cl4
PCl3
PCl5 | S2Cl2
SCl2
SCl4 | Cl2 | Ar
KCl | CaCl
CaCl2 | ScCl3 | TiCl2
TiCl3
TiCl4 | VCl2
VCl3
VCl4
VCl5 | CrCl2
CrCl3
CrCl4 | MnCl2 | FeCl2
FeCl3 | CoCl2
CoCl3 | NiCl2 | CuCl
CuCl2 | ZnCl2 | GaCl2
GaCl3 | GeCl2
GeCl4 | AsCl3
AsCl5 | Se2Cl2
SeCl4 | BrCl | KrCl
RbCl | SrCl2 | YCl3 | ZrCl3
ZrCl4 | NbCl4
NbCl5 | MoCl2
MoCl3
MoCl4
MoCl5
MoCl6 | TcCl4 | RuCl3 | RhCl3 | PdCl2 | AgCl | CdCl2 | InCl
InCl2
InCl3 | SnCl2
SnCl4 | SbCl3
SbCl5 | Te3Cl2
TeCl4 | ICl
ICl3 | XeCl
XeCl2
CsCl | BaCl2 |  | HfCl4 | TaCl5 | WCl2
WCl3
WCl4
WCl5
WCl6 | Re3Cl9
ReCl4
ReCl5
ReCl6 | OsCl4 | IrCl2
IrCl3
IrCl4 | PtCl2
PtCl4 | AuCl
AuCl3 | Hg2Cl2,
HgCl2 | TlCl | PbCl2,
PbCl4 | BiCl3 | PoCl2,
PoCl4 | AtCl  | RnCl2
FrCl | RaCl2 |  | Rf  | Db  | Sg  | Bh  | Hs  | Mt  | Ds  | Rg  | Cn  | Nh  | Fl  | Mc  | Lv  | Ts  | Og
| ↓  |  |
LaCl3 | CeCl3 | PrCl3 | NdCl2,
NdCl3 | PmCl3 | SmCl2,
SmCl3 | EuCl2,
EuCl3 | GdCl3 | TbCl3 | DyCl2,
DyCl3 | HoCl3 | ErCl3 | TmCl2
TmCl3 | YbCl2
YbCl3 | LuCl3
AcCl3 | ThCl4 | PaCl5 | UCl3
UCl4
UCl5
UCl6 | NpCl4 | PuCl3 | AmCl2
AmCl3 | CmCl3 | BkCl3 | CfCl3 | EsCl3 | Fm  | Md  | No  | LrCl3

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