Bis(triphenylphosphineoxide) manganese(III) chloride

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manganese(III) chloride, bis(triphenylphopshine oxide)
(MnCl3(OPPh3)2).png
Trichloridobistriphenylphosphineoxidemanganese(III).jpg
Names
Systematic IUPAC name
trichloridobis(triphenylphopshineoxide)manganese(III)
Other names
MnCl3(OPPh3)2
Identifiers
3D model (JSmol)
  • InChI=1S/2C18H15OP.3ClH.Mn/c2*19-20(16-10-4-1-5-11-16,17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;;/h2*1-15H;3*1H;/q;;;;;+3/p-3
    Key: QFCMPBNNKDBSLH-UHFFFAOYSA-K
  • [Mn+3].[Cl-].[Cl-].[Cl-].O=P(c1ccccc1)(c2ccccc2)c3ccccc3.O=P(c1ccccc1)(c2ccccc2)c3ccccc3
Properties
C36H30Cl3MnO2P2
Molar mass 717.87 g·mol−1
Appearanceblue solid
Melting point 140 °C (284 °F; 413 K) (with decomposition)
μeff = 4.96 μB.H. (solid-state), 4.83 μB.H. (DCM)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Bis(triphenylphosphineoxide) manganese(III) chloride is a coordination complex of manganese(III) chloride. Unlike most compounds containing "Mn(III)Cl3", [MnCl3(OPPh3)2] can be stored under normal laboratory conditions. [1] It is a blue, paramagnetic solid.

Synthesis and reactions

Treatment of meta-stable solutions of Mn(III)Cl3 with triphenylphosphine oxide results in precipitation of solid [MnCl3(OPPh3)2]. This compound was first prepared using the thermally unstable ethereal adduct (dioxane)Mn(III)Cl3. [2] A convenient synthesis starts from Mn(OAc)2, trimethylsilylchloride, and potassium permanganate. [3]

Synthesis of MnCl3(OPPh3)2.png

[MnCl3(OPPh3)2] can be used as a starting material in coordination chemistry. [3]

Coordination with MnCl3(OPPh3)2.png

[MnCl3(OPPh3)2] can also be used as a stoichiometric reagent in alkene dihalogenation reactions. [3]

Alkene dichlorination with MnCl3(OPPh3)2.png

Related Research Articles

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2
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2
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4
, the conjugate base of permanganic acid. Because the manganese atom is in the +7 oxidation state, the permanganate(VII) ion is a strong oxidizing agent. The ion is a transition metal oxo complex with tetrahedral geometry. Permanganate solutions are purple in color and are stable in neutral or slightly alkaline media. The exact chemical reaction is dependent upon the organic contaminants present and the oxidant utilized. For example, trichloroethane (C2H3Cl3) is oxidized by permanganate ions to form carbon dioxide (CO2), manganese dioxide (MnO2), hydrogen ions (H+), and chloride ions (Cl).

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3
COCHCOCH
3
) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
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References

  1. Goedecke, Catharina (2022-09-08). "Bench-Stable Manganese(III) Chloride Source". ChemistryViews. Retrieved 2022-09-08.
  2. Uson, R.; et al. (1976). "Pentacoordinate Neutral Manganese(III) Complexes". Transition. Met. Chem. 1 (3): 122–126.
  3. 1 2 3 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. PMID   36067378. S2CID   252110339.