PREPARATION OF THE PARAMAGNETIC COMPLEX Mn(acac)3 BY CHEYENNE MARTINS SUBMITTED 10/10/2012

ABSTRACT The purpose of this experiment was to create Mn(acac)3 and then figure out its normal spinstate (i.e. low or high spinparamagnetic or diamagnetic) through testing by Evans method. Approximately 72% of Mn(acac)3 was formed; a relatively high yield. There were four unpaired electrons calculated from experimental data, indicating that Mn(acac)3 was a high-spin molecule. These two pieces of data in conjunction with literature values indicate the success of the experiment. Based on the experimental data and the molecules octahedral (D3) structure, its configuration would be (t2g)3(eg)1. INTRODUCTION Electrons can exist in a paramagnetic or diamagnetic state. Elements containing unpaired electrons are known to have a strong field; the same is true vice versa. Electrons with paired electrons usually have a weak field. The number of unpaired electrons is useful in multiple ways: it is closely related to the oxidation state of the metal, and it can be used to determine the geometries of molecules in question. Mn(acac)3 is also known as tris(acetylacetonato)manganese(III). Acetylacetonate (Hacac) is a bidentate ligand with a charge of negative one. When attached to manganese, it gives it an octahedral geometry but with D3 group symmetry1. The purpose of this experiment is to first synthesize this compound, Mn(acac)3, and then subsequently measure the magnetic susceptibility by the Evans method. Compound formation will proceed according to the equation, 4 KMnO4 + 12 C5H8O2 + 2 H2O = 4 Mn(C5H8O2)3 + 4 KOH + 7 O2. Magnetic susceptibility will be measured through NMR analysis of the product. EXPERIMENTAL SECTION PROCEDURE Exactly 0.375 grams of KMnO4 were weighed and added to a 25mL Erlenmeyer flask filled with 7.5 mL of H2O. The solution was heated to 80oC and then allowed to cool to room temperature. Once cooled, 1.7 mL of acetylacetonate was carefully added and the solution boiled once more. After 5 minutes, the solution was removed from the hot plate and subsequently cooled in an ice bath. Vacuum

filtration was performed, crystals were collected and weighed, and NMR analysis was performed with both the product (Mn(acac)3) and the solvent (CHCl3). EXPERIMENTAL SECTION RESULTS Observations KMnO4 Compound Purple-blackish +H2O Purple-blackish Precipitate Black

NMR CHCl3 Mn(acac)3

Peak 7.636 ppm 8.476 ppm

Compound PPT Theoretical Yield Percent Yield Xm/cm3mol-1 X/ cm3mol-1 n (unpaired e-s) eff/magnetons

Mn(acac)3 0.640 g 0.843 g 72.92% 14.1*10-3 14.16*10-3 4.84 5.76

Reactions 4 KMnO4 + 12 C5H8O2 + 2 H2O 4 Mn(C5H8O2)3 + 4 KOH + 7 O2 Mn(C5H8O2)3 + CHCl3 MnCl(C5H8O2)2 + CHCl2+ + C5H8O2Calculations Theoretical Yield:
( )

= 1.971 grams needed

Therefore KMnO4 is the limiting reactant, not Hacac. So

( ) ( )

= 0.843 grams

Percent Yield:

100% = 75.92% yield Molar Susceptibility: ( (

( )

) ) where ( ) ( (

14.16* ( n2 + 2n - 33.2 = 0

) where T = 293Ksolving for n

= 4.8 unpaired electrons = 5.76

eff = DISCUSSION

From ligand field theory, we know that acac has a charge of negative one due to resonance. As a result, manganese has an oxidation state of +3. Therefore, its d-count is d4. Based on the previous calculations, the number of unpaired electrons was predicted to be between 4 and 5 (obtained value of approx. 4.8). As the value of 5 is theoretically impossible (it doesnt have 5 electrons), its therefore reasonable to conclude that Mn(acac)3 is a high spin molecule and is thus paramagnetic. Its configuration would be (t2g)3(eg)1. This is derived also from its structure: its octahedral (D3 theoretically, D3h with distortion), leaving its orbital splitting to be three below two (and its symmetry labels to be t2g and eg respectively. If Mn(acac)3 was a low spin molecule, there would be only one unpaired electron. The experimental data disproves the existence of this state. Because Mn(acac)3 is a high-spin molecule

and readily reacted with chloroform to form MnCl(C5H8O2)2, it can be concluded that Mn(acac)3 can function as an oxidant. Previous experiments2 confirm that Mn(acac)3 is a high-spin molecule, and as a result, it can be concluded that this experiment had a high purity level, despite the slightly off n number obtained. Likely, a little more sample than was recorded was tested in NMRthus throwing off calculations by a marginal amount. Other data obtained was XM (at 14.10 cm3/mol) and X (at 14.16 cm3/mol). Literature values were unable to be obtained, so these values will not be directly commented on. However, due to the fact that the unpaired electrons (the number of which was derived from the aforementioned numbers) is extremely close to previous experimental data,2 its reasonable to conclude that XM and X' are accurate as well. Percent yield was relatively high at approximately 72%. Errors could have occurred during vacuum filtration (product still left in the funnel), decreasing yield. CONCLUSION In conclusion, percent yield was relatively high at approximately 72%. Mn(acac)3s geometry (as an ideally D3 octahedral complex) in collaboration with experimental data (unpaired electrons n 4.8) indicate that it is paramagnetic. In other words, Mn(acac)3 is a high spin state with a configuration of (t2g)3(eg)1. Its d-count would be 4, leaving manganese with an oxidation state of +3. All things considered, the experiment could be considered a success. REFERENCES 1. Angelici, Girolami, Rauchfuss, in: Synthesis and Techniques in Inorganic Chemistry A LABORATORY MANUAL. 2. Bayburt, Sharp, in: Electron- and nuclear-spin relaxation in an integer spin system, tris-(acetylacetonato )Mn(III) in solution, 1990.

POST LAB 1. Theres an increase in d-count which could indicate an increase in shielding due to an increase in size and an increase in bonding ligands. 2. HgCo(NCS)4 has 3 unpaired electrons and is octahedral. [Ni(en)3]S203 has two unpaired electrons with octahedral geometry . 3. No, you would need more information so that you could calculate X. 6. The presence of oxygen, which is paramagnetic. 9. Ni(CN)42- is diamagnetic, as indicated by a magnetic moment of zero. As a result, it is square square planar. NiCl42- is paramagnetic and therefore is tetrahedral with a d-count of 10. Its orbital splitting would be 2 below 3, with a single electron in each.