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1982 669

Direct Synthesis of Tris(acetylacetonato)manganese( 111)

By Manabendra N. Bhattacharjee and Mihir K. Chaudhuri,' Department of Chemistry, North-Eastern Hill
University, Shillong 793 003, India
Darlando T. Khathing, Department of Physics, North-Eastern Hill University, Shillong 793 003,India

A concentrated solution of K[Mn04] undergoes a ready reaction with acetylacetone, in the absence of any buffer,
giving a very high yield of the title compound, [Mn(acac)J. The pH of the solution, recorded immediately after
the formation of crystalline [Mn(acac),], was found to be ca. 5. Electron impact induced mass spectrometry
showed the compound to be monomeric.
Published on 01 January 1982 on http://pubs.rsc.org | doi:10.1039/DT9820000669

TRIS(ACETYLACETONATO) MANGANESE (111) , [Mn(acac)J, was stirred for ca. 5 min over a steam-bath and then allowed
has been known for a long time. The compound can be to cool for ca. 10 min. The dark brown-black shiny crystals
synthesised by air or chlorine oxidation of a basic solu- of [Mn(acac),] were filtered off and washed several times with
small amounts of acetylacetone-water (1 : 1) and finally
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tion of Mn2+in the presence of acetylacetone. However,

dried in vacuo. The compound thus obtained was very
this method has not been used in practice because of the
pure and gave extremely satisfactory analysis. If desired,
deleterious effect of alkali on the end product, as well as the compound can be recrystallised by dissolving it in the
the chances of its contamination by chloride ions. minimum volume of hot benzene followed by the addition of
Instead, the syntheses due to Cartledge and Charles
involving the oxidation of Mn2+ with K[MnO,] in the Mass spectral data for [Mn(acac),]
presence of acetylacetone (Hacac) have been employed. (a) Major peaks
The success of this method depends markedly on the Intensity
pH. The reaction mixture requires to be regulated at Assignment mlz (%)
pH ca. 5 by the addition of a large amount of sodium [Mn(C,H70z)31+ 362 18
[Mn(c~&Oz)z1+ 253 100
acetate. The use of sodium acetate in such quantities [Mn(CsH70z) (C4H40z)lf 238 34
must surely contaminate the end product. In the [Mn(CsH7Oz)I+ 164 74
course of our studies on the synthesis of manganese(II1) [Mn(C*H,O,)l+ 139 6

--
Mn+ 65 0
compounds directly from K[Mn04],3we have developed
(b) Metastable transitions
a method for the synthesis of [Mn(acac),] which does
not require buffer. This note reports the direct synthesis mlz
Fragment
of [Mn(acac),]. Observed Calculated Process lost
181.8 181.84 352 ---t 253 C,H?O,
223.9 223.89 253 -+ 238 CH3
EXPERIMENTAL 99.6 99.65 238 * 154 C4H40,
Reagent-grade potassium permanganate and acetyl- 125.6 125.46 154 * 139 CH3
acetone were used in the synthesis. Infrared spectra were
hot light petroleum (b.p. 40-60 "C) and then cooling at
recorded on a Perkin-Elmer model 125 spectrophotometer.
ca. 0 "C. The yield obtained was 9.7 g (87%). The com-
The oxidation state of manganese in the compound was
pound does not have a sharp melting point but decomposes
determined iodometrically by reduction of a known amount
a t ca. 155 "C. This method may also be used for large-
of the compound with acidified potassium iodide solution
scale synthesis (Found: C, 51.1; H, 6.10; Mn, 15.7. Calc.
followed by titration of the liberated iodine with standard
for C,,H,,MnO,: C, 51.15; H, 6.00; Mn, 15.6%). The
sodium thiosulphate solution.
molecular weight was found to be 352 mass spectrometric-
The mass spectrum was recorded on a Varian MAT CH-5
mass spectrometer. The sample was introduced into the ally.
ionisation chamber using a direct insertion probe. The
operation conditions were electron energy, t 70 eV ; source RESULTS A N D DISCUSSION
temperature, 20 "C; resolution, 1 000; and accelerating Direct Synthesis.-In our previous paper we emphas-
voltage, 8 kV. The essential features of the mass spectrum
run at 20 "C are given in the Ta-ble. The mass spectro-
ised the role of acetylacetone as a reducing agent in the
metric observations were made with the field of ionising reduction of MnVII. We have now extended the use of
current sufficiently strong to trap primary ions. this concept to the synthesis of [Mn(acac),]. The
Synthesis of Tris(acetylacetonato)manganese(m),[Mn- method described leads to the rapid synthesis of tris-
(acac),].-A quantity of powdered K[Mn04] (5.0 g, 31.7 (acetylacetonato)manganese(III) in very high yield and
mmol) was dissolved in the minimum volume of water by analogous procedures have also been used successfully
slight warming over a steam-bath and the solution then for the synthesis of [Cr(acac),] from CrO, and [Ni(acac),-
filtered. Distilled acetylacetone (22.0 g, 220.0 mmol) was (H,O),] from NiO(0H). Gram quantities of [Mn-
added to the solution with vigorous stirring. The mixture (acac),] can be synthesised in less than 1 h without
t Throughout this note: 1 eV x 1.60 x lo-'* J . using any buffer. The reduction of [Mn04]- by acetyl-
 View Article Online
J.C.S. Dalton
acetone and the subsequent formation of the tris chelate good mass spectra of [Mn(acac)J have not always
owing to the presence of an excess of acetylacetone been su~cessful.~It appears that the spectra of tris-
(Hacac) appear to be the driving forces for the reaction. (acety1acetonato)metalates markedly depend on the
Although the present synthesis does not involve any method of sample introduction. We favoured the direct
buffer, the course of the reaction is such that it auto- insertion probe and introduced the sample into the ionis-
matically maintains the pH desired for the successful ation chamber without any prior heating. The other
formation of [Mn(acac)J. The pH of the solution conditions were similar to those maintained in our
measured immediately after the formation of the com- earlier experiments.
pound was found to be ca. 5. This value concurs The spectrum run a t 20 "C (Table) showed a molecular
exactly with that maintained by the addition of a large ion signal of moderate intensity (18%) at m/z 352 and a
amount of sodium acetate in the syntheses of Cartledge

(C,H70,)]+
+- --
base peak a t m/x 253 due to [Mn(acac),]+, the major
and Charles.2 It is not possible to propose a mechanism fragmentation path being [Mn(C5H70,),]+-+ [Mn-
for the present synthesis in the absence of full details of (C5H702)2] [Mn(C5%02) (C4H402)I
[Mn(C4H40,)]+
+ [Mn-
Mn+. The meta-
Published on 01 January 1982 on http://pubs.rsc.org | doi:10.1039/DT9820000669

the oxidised products of acetylacetone.

Characterisation. -Tris (acetylacet onat0)manganese- stable peaks observed a t m/z * 181.8, 223.9, 99.6, and
(111) is a dark brown-black crystalline compound, un- 125.6 support the proposed fragmentation path and
stable in air but capable of being stored in a sealed closely resemble those reported by Westmore and co-
container for months. The compound is slightly soluble w o r k e r ~ . ~
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in water but dissolution is accompanied by decomposi- [1/1076 Received, 7th JuZy, 19811
tion. Freshly prepared [Mn(acac),] does not show a REFERENCES
sharp melting point but decomposes around 165 "C.
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shows the characteristics of chelated acctylacetonates R. G. Charles, Inorg. Synth., 1966, 7 , 183.
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of various forms of [Mn(acac)J which also showed the B. R. Stults, R. S. Marianelli, and V. W. Day, Inovg. Chem.,
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synthesised compound gave +111, providing further * M. K. Chaudhuri, H. S. Dasguyta, N. Roy, and D. T.
Khathing, Org. Mass Spectrom., 1981, 16, 303.
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