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Tris(acetylacetonato)manganese (III) is one of numerous
organometallic compounds. Other name of this compound is
Manganese(III) acetylacetonate
Manganic acetylacetonate
3-Penten-2-one, 4-hydroxy-, manganese(3+) salt
Mangan(3+)tris[(2Z)-4-oxo-2-penten-2-olat]
3-Penten-2-one, 4-hydroxy-, manganese(3+) salt, (3Z)-
(3:1)
General formula: Mn(acac)3
:
 Structure: distorted octahedral structure (JTD)
 Point group: → d3 pseudo Oh symmetry
 melting point: 159-161 °C not sharply
 Decomposed start at above 150 oC
 Boiling point: 187-188 °C
 Molecular waight: 352.28 g/mol
 Colour: black to dark brown by reflected light
green by transmitted light
 Molecular formula: C15H24MnO6
 Compound is Canonicalized
 Soluble in benzene, chloroform,
ethyl acetate and less soluble in water
 One electron oxidant
 Oxidation state of cental metal (Mn)= +3
 Coordination number = 6
 Electronic configuration of Mn3+ = [Ar]3d4
 Hybridization of complex= sp3d2
 Structure: octahedral
 Orbital of metal that are present in hybrization is
 Type of ligand = –ve charge bidentad ligand (weak field
ligand)
 Number of unpair electron in central metal =4
4S 4px 4py 4pz
4dx
2
-y
2
4dz
2
Orbital in Mn3+
:
:
:
:
:
:
acac ligand
4s 4px 4py 4pz
4dx2-y2
4dz2
O
OH
+ B
O
O
+ BH
O
O
HAcac Acac
Synthesis of ligand
Ligand
O
O
O
O
Acac is bidented ligand with resonance form
so this is AA type ligand
 Oxidation state of cental metal (Mn)= +3
 Electronic configuration of Mn3+ = [Ar]3 d4
 Type of ligand= weak field ligand
 type of complex= high sspin complex
 Number of unpair electron= 4
 Possible transition= d-d transition eg
 It show jtd
t2g
Cfse value =
3/5
3p
t2g
eg
5D
5Eg
5T2g
potassium
permanganate
acetylacetone
distilled water
potassium
permanganate
manganese(II)
chloride
acetylacetone
sodium acetate
trihydrate
Distilled water
potassium
permanganate
acetylacetone
manganese(II)
chloride
Distilled water
potassium
permanganate
acetylacetone
MnSO4
Distilled
water
dark shiny crystals of Mn(acac)3 was filtered off.
dried in vacuum over fused CaCl2 for 15
minutes
Mn(acac)3 synthesized
distilled acetylacetone are mix in solution with continuous stirring.
A white crystalline precipitates were
observed
cool down the solution
5 g of KMnO4 in 50 mL of distilled water with continuous stirring
Give heat Solution ready
KMnO4 + 4(Hacac) → [Mn(acac)3] + 2H2O + Kacac + O2
sodium acetate trihydrate (2.6 g dissolved in a minimal amount of water) to the reaction mixture.
Heat the resulting mixture directly on a
hotplate for 10 minutes at about 70°C
cool at room temperature Collect the dark
brown precipitate using a Büchner funnel
Make another solution of 200 mg of KMnO4 in 10 mL of distil water, with continue stirring
add the solution dropwise to the mixture of
MnCl 2•4H2O and sodium acetate trihydrate.
stirring the mixture five minutes
1.0 g of MnCl2•4H2O and 2.6 g of sodium acetate trihydrate desolve in minimum ammount of
distil water
continuous stirring
Solution ready 4.0 mL of acetylacetone with
continued stirring.
4MnCl2 + 15HC5H7O2+ KMnO4+ 4NaC2H3O2  5Mn(C5H7O2)3 + KC2H3O2 +4NaCl
dark shiny crystals of Mn(acac)3 was filtered off.
dried in vacuum over fused CaCl2 for 15
minutes
Mn(acac)3 synthesized
1.7g acetylacetone and 0.4 g Mn(Cl)2 are mix in solution with continuous stirring.
A white crystalline precipitates were
observed
cool down the solution
0.1 g of KMnO4 in 50 mL of distilled water with continuous stirring
Give heat Solution ready
4MnCl2.4H2O + KMnO4 + 15(Hacac) → 5[Mn(acac)3] + 20H2O + 7HCl + KCl
dark shiny crystals of Mn(acac)3 was filtered off.
dried in vacuum over fused CaCl2 for 15
minutes
Mn(acac)3 synthesized
7.5g acetylacetone and 2g MnSO4 are mix in solution with continuous stirring.
A white crystalline precipitates were
observed
cool down the solution
Give heat Solution ready
 (i) the presence of strong absorption bands (peaks nos. 14, 15, and 16) at 1588, 1514.8, and
1384.6 cm-1 respectively (C–O, carboxylate),
 (ii) peak no. 23 at 753.5 cm-1,
 (iii) peak no. 26 at 565 cm-1 (Mn–O, stretching).
NMR data of Mn(acac)3
 the metallic content of Mn% in solid crystals of product was 14.7%, as confirmed
by EDXRF, whereas
 the organic carbon content was 50.21% as analyzed by the elemental
analysis showed the EDIX chart for produced crystals
Application
of
Mn(acac)3
Synthesis of
other Mn3+
salt
Organic
synthisis
polymersition
Polarographic
data
Electronics
davise as
cell
Voltammeteric
data
Mn(acac)3 is a useful starting material for the preparation of
other Mn(III) compounds.
Mn(acac)3 is 1 electron oxidant so its used to oxidize
phenols, β-dicarbonyl compounds, and thiols to the
corresponding radical. example
Mn(acac)3 has been used for the intramolecular oxidative coupling examples
Mn(acac)3 induces the oxidative cyclization of a phenolic oxime to give the
spiroisoxazoline in 50% yield
2-naphthol is oxidized to 2,2-binaphthol in 69% yield in acetonitrile or carbon disulfide
Peroxy hemiacetals are prepared by oxidative addition of Mn(acac)3 to alkenes in the
presence of oxygen
Application
The Mn(acac)3 complex can be oxidized to [Mn(acac)3]+ and
reduced to [Mn(acac)3]− at a glassy carbon electrode.
Mn(III)(acac)3 + e− ↔ [Mn(II)(acac)3] −
E = −0.4 V
Mn(III)(acac)3 ↔ [Mn(IV)(acac)3] + + e−
E = 0.7 V
Half cell potential of Mn(acac)3 in different solvent
solvent Half cell potential
Tetrahydrofurane (THF) 1.22
Methanol (MeOH) 1.30
Dichloromethane (DCM) 1.30
Propylenecarbonate (PC) 1.45
Acetonitrile (CH3CN) 1.49
N,N-Dimethylformamide
(DMF)
1.2
Application
Mn(acac)3 creat free radical who starts polymerisation
The sensitivity of the half-wave potentials of Mn(acac)3 to'the addition of salts
necessitated a special technique in obtaining polarographic and voltammetric data.
Application
Other reaction using Mn(acac)3
Application
 Harmful if swallowed [Warning Acute toxicity, oral]
 Causes skin irritation [Warning Skin
corrosion/irritation]
 Causes serious eye irritation [Warning Serious eye
damage/eye irritation]
property of Tris(acetylacetonato)manganese(III)

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property of Tris(acetylacetonato)manganese(III)

  • 2. Tris(acetylacetonato)manganese (III) is one of numerous organometallic compounds. Other name of this compound is Manganese(III) acetylacetonate Manganic acetylacetonate 3-Penten-2-one, 4-hydroxy-, manganese(3+) salt Mangan(3+)tris[(2Z)-4-oxo-2-penten-2-olat] 3-Penten-2-one, 4-hydroxy-, manganese(3+) salt, (3Z)- (3:1) General formula: Mn(acac)3
  • 3. :  Structure: distorted octahedral structure (JTD)  Point group: → d3 pseudo Oh symmetry  melting point: 159-161 °C not sharply  Decomposed start at above 150 oC  Boiling point: 187-188 °C  Molecular waight: 352.28 g/mol  Colour: black to dark brown by reflected light green by transmitted light  Molecular formula: C15H24MnO6  Compound is Canonicalized  Soluble in benzene, chloroform, ethyl acetate and less soluble in water  One electron oxidant
  • 4.  Oxidation state of cental metal (Mn)= +3  Coordination number = 6  Electronic configuration of Mn3+ = [Ar]3d4  Hybridization of complex= sp3d2  Structure: octahedral  Orbital of metal that are present in hybrization is  Type of ligand = –ve charge bidentad ligand (weak field ligand)  Number of unpair electron in central metal =4 4S 4px 4py 4pz 4dx 2 -y 2 4dz 2
  • 5. Orbital in Mn3+ : : : : : : acac ligand 4s 4px 4py 4pz 4dx2-y2 4dz2
  • 6. O OH + B O O + BH O O HAcac Acac Synthesis of ligand Ligand O O O O Acac is bidented ligand with resonance form so this is AA type ligand
  • 7.  Oxidation state of cental metal (Mn)= +3  Electronic configuration of Mn3+ = [Ar]3 d4  Type of ligand= weak field ligand  type of complex= high sspin complex  Number of unpair electron= 4  Possible transition= d-d transition eg  It show jtd t2g Cfse value = 3/5
  • 10. potassium permanganate acetylacetone distilled water potassium permanganate manganese(II) chloride acetylacetone sodium acetate trihydrate Distilled water potassium permanganate acetylacetone manganese(II) chloride Distilled water potassium permanganate acetylacetone MnSO4 Distilled water
  • 11. dark shiny crystals of Mn(acac)3 was filtered off. dried in vacuum over fused CaCl2 for 15 minutes Mn(acac)3 synthesized distilled acetylacetone are mix in solution with continuous stirring. A white crystalline precipitates were observed cool down the solution 5 g of KMnO4 in 50 mL of distilled water with continuous stirring Give heat Solution ready KMnO4 + 4(Hacac) → [Mn(acac)3] + 2H2O + Kacac + O2
  • 12. sodium acetate trihydrate (2.6 g dissolved in a minimal amount of water) to the reaction mixture. Heat the resulting mixture directly on a hotplate for 10 minutes at about 70°C cool at room temperature Collect the dark brown precipitate using a Büchner funnel Make another solution of 200 mg of KMnO4 in 10 mL of distil water, with continue stirring add the solution dropwise to the mixture of MnCl 2•4H2O and sodium acetate trihydrate. stirring the mixture five minutes 1.0 g of MnCl2•4H2O and 2.6 g of sodium acetate trihydrate desolve in minimum ammount of distil water continuous stirring Solution ready 4.0 mL of acetylacetone with continued stirring. 4MnCl2 + 15HC5H7O2+ KMnO4+ 4NaC2H3O2  5Mn(C5H7O2)3 + KC2H3O2 +4NaCl
  • 13. dark shiny crystals of Mn(acac)3 was filtered off. dried in vacuum over fused CaCl2 for 15 minutes Mn(acac)3 synthesized 1.7g acetylacetone and 0.4 g Mn(Cl)2 are mix in solution with continuous stirring. A white crystalline precipitates were observed cool down the solution 0.1 g of KMnO4 in 50 mL of distilled water with continuous stirring Give heat Solution ready 4MnCl2.4H2O + KMnO4 + 15(Hacac) → 5[Mn(acac)3] + 20H2O + 7HCl + KCl
  • 14. dark shiny crystals of Mn(acac)3 was filtered off. dried in vacuum over fused CaCl2 for 15 minutes Mn(acac)3 synthesized 7.5g acetylacetone and 2g MnSO4 are mix in solution with continuous stirring. A white crystalline precipitates were observed cool down the solution Give heat Solution ready
  • 15.  (i) the presence of strong absorption bands (peaks nos. 14, 15, and 16) at 1588, 1514.8, and 1384.6 cm-1 respectively (C–O, carboxylate),  (ii) peak no. 23 at 753.5 cm-1,  (iii) peak no. 26 at 565 cm-1 (Mn–O, stretching).
  • 16. NMR data of Mn(acac)3
  • 17.  the metallic content of Mn% in solid crystals of product was 14.7%, as confirmed by EDXRF, whereas  the organic carbon content was 50.21% as analyzed by the elemental analysis showed the EDIX chart for produced crystals
  • 19. Mn(acac)3 is a useful starting material for the preparation of other Mn(III) compounds. Mn(acac)3 is 1 electron oxidant so its used to oxidize phenols, β-dicarbonyl compounds, and thiols to the corresponding radical. example
  • 20. Mn(acac)3 has been used for the intramolecular oxidative coupling examples Mn(acac)3 induces the oxidative cyclization of a phenolic oxime to give the spiroisoxazoline in 50% yield
  • 21. 2-naphthol is oxidized to 2,2-binaphthol in 69% yield in acetonitrile or carbon disulfide Peroxy hemiacetals are prepared by oxidative addition of Mn(acac)3 to alkenes in the presence of oxygen Application
  • 22. The Mn(acac)3 complex can be oxidized to [Mn(acac)3]+ and reduced to [Mn(acac)3]− at a glassy carbon electrode. Mn(III)(acac)3 + e− ↔ [Mn(II)(acac)3] − E = −0.4 V Mn(III)(acac)3 ↔ [Mn(IV)(acac)3] + + e− E = 0.7 V Half cell potential of Mn(acac)3 in different solvent solvent Half cell potential Tetrahydrofurane (THF) 1.22 Methanol (MeOH) 1.30 Dichloromethane (DCM) 1.30 Propylenecarbonate (PC) 1.45 Acetonitrile (CH3CN) 1.49 N,N-Dimethylformamide (DMF) 1.2 Application
  • 23. Mn(acac)3 creat free radical who starts polymerisation The sensitivity of the half-wave potentials of Mn(acac)3 to'the addition of salts necessitated a special technique in obtaining polarographic and voltammetric data. Application
  • 24. Other reaction using Mn(acac)3 Application
  • 25.  Harmful if swallowed [Warning Acute toxicity, oral]  Causes skin irritation [Warning Skin corrosion/irritation]  Causes serious eye irritation [Warning Serious eye damage/eye irritation]