Part II Ligand Field Theory

Experiment 6

Magnetochemistry: Synthesis and Determination of the Magnetic Moment of Some Iron and Nickel Complexes
Introduction Many transition-metal complexes are paramagnetic, due to the presence on unpaired d electrons. Ligand field theory can be used to account for the number of unpaired d electrons that occur for any specific compound. The underlying principles of ligand field theory have already been developed. In particular, magnetic measurements can distinguish between two possible arrangements of the d electrons in the common Td and Oh geometries, called high-spin and lowspin. For example, Figure 6-1 illustrates the consequences of the two environments for an octahedral d5 system. Typically, high-spin complexes occur when the size of 0 is of the same order of magnitude as the electron spin-pairing energy.
OCTAHEDRAL - HIGH SPIN e
g

OCTAHEDRAL - LOW SPIN eg

0
t2g t2g

Figure 6-1 Ligand field splitting diagram for high and low spin octahedral environments However, when 0 >> spin-pairing energy, the low-spin arrangement will be preferred. For any given metal and oxidation state, the size of 0 is largely determined by the nature of ligand, and especially of the identity and charge of the donor atoms in the ligands. The way in which magnetochemistry can be used to distinguish the two cases is explained further below. In this experiment you will measure the magnetic moments of four metal complexes, including some which are commercial reagents. The structures of these complexes are given in Figure 6-2.

Bulk magnetic behaviour Much of van Vleck's early work on crystal field theory focused on interpreting the magnetic behaviour of transition-metal compounds (which of course include the most important bulk magnetic materials such as iron, cobalt, and magnetite, Fe3O4). The origin of all magnetic phenomena can be traced to the motion of charges. Electrons moving in a circular path in an atom or molecule are constantly undergoing acceleration (because of the circular motion), and therefore, generate a magnetic field perpendicular to their direction of motion, the orbital magnetic moment. Electrons also have a spin, as a simplification visualized by the rotation of the electron around its own axis, which produces a spin magnetic moment. If the electrons are paired in a wavefunction, their spin magnetic fields are equal and opposite (spin paired). If these moving electrons are placed into a large external magnetic field (the applied magnetic field), Chemistry 3820 Laboratory Manual Page6-1

Part II Ligand Field Theory

N C N C K3 C N C N Fe C N O O N C O Fe O O O

Experiment 6

NH2 N K3 C N N C Ni C N NH2 NH2 C NH2 Ni NH2 NH2 S 2O 3

Figure 6-2 Structures of the metal complexes measured in this experiment

then the external field induces an additional current that causes a magnetic field by itself. This induced magnetic field is opposite to the external magnetic field (Lenz law). As a consequence, the magnetic field (actually, B is the magnetic flux density, H is the magnetic field strength) inside the sample (Binternal) will be weaker than the external field (Bexternal), with B being negative, and the sample is repelled by the applied field. Binternal = Bexternal + B This magnetic behaviour is called diamagnetism. Every paired electron contributes to the diamagnetism of a substance. Hence, diamagnetism is present in every sample. The equation can be rewritten in two different ways: Binternal = r Bexternal with r as the relative magnetic permeability or Binternal = (1+ V) Bexternal and B = V Bexternal with V as the magnetic susceptibility (volume susceptibility) The formulation using susceptibilities is more commonly used among magnetochemists and will be used for this experiment. For diamagnetic samples, V is negative. The size of the diamagnetic susceptibility is a function of the number of electrons and the radius of the electron orbits. Instead of the additional magnetic flux density, B, the magnetization M (in A/m) is generally used: B = 0 M (0 is the magnetic field constant). With Bexternal = 0 Hexternal substitution the above equation yields M = V Hexternal. If an orbital is singly occupied, a small magnetic moment is associated with the unpaired electron. This magnetic moment aligns itself with an external magnetic field and increases the magnetic field inside the sample. As a consequence, this sample is drawn into the magnetic field. Chemistry 3820 Laboratory Manual Page6-2

Part II Ligand Field Theory

Experiment 6

This effect is called paramagnetism. This causes a net attraction between paramagnets and magnetic field gradients. The paramagnetic contribution is two orders of magnitudes larger than the diamagnetic contributions. Therefore, one unpaired electron as a paramagnetic centre will overshadow the diamagnetism of all the paired electrons in the sample. For paramagnetic substances, B and the paramagnetic susceptibility are positive. Macroscopic magnetic effects are caused by the additive (cooperative) effect of atomic paramagnets. If every second paramagnet in a material is aligned in an opposing fashion, the bulk material is said to be antiferromagnetic. If on the other hand they align in the same direction, the bulk material is ferromagnetic. Permanent iron magnets are common examples of ferromagnetic materials. The magnetic susceptibility is a measure of the force with which magnetic attractions or repulsions occur. The relevant scale in the old, but commonly used cgs units of magnetic susceptibility is given in Table 6-1. The susceptibilities in SI units and cgs units differ by a factor of 4: (SI) = 4 (cgs).

Table 6-1 Classification of magnetic behaviour Type of magnetism diamagnetism paramagnetism ferromagnetism antiferromagnetism Susceptibility, ( cgs units) -10
-6 -6

Field dependence independent of H independent of H dependent on H

100 10 10 - 10
-2

-4 -6

1 to 100 10

often dependent on H

The total magnetic susceptibility of the substance will be the sum of all the diamagnetic and paramagnetic contributions from all the electrons in the sample. When these are oriented at = dia + para random, the measurement of the bulk sample is akin to measuring the average susceptibility of a single formula unit. All our measurements will be made on finely ground powders, which can safely be assumed to be totally randomly distributed. The volume susceptibility, V, is defined by the equation: dH F = 0 V V H dx The integration of this equation relates the force, F, experienced by the sample over the integrated field strength. Since weighing a sample is equivalent to measuring the force of gravity acting on it, we can use the weight of the sample compared to its apparent weight in a magnetic field to measure . Rather than solving this equation directly, which would require the difficult job of measuring the integrated field strength over the volume of space the sample occupies, we use a standard of known measured under identical conditions to get for our unknown material.

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Part II Ligand Field Theory

Experiment 6

Several of the seemingly laborious restrictions described below result directly from this theory: (1) the tube must always be suspended at exactly the same height, and the contents must always be filled to exactly the same level - otherwise the integrated field strength will not be the same. (2) Air contains paramagnetic oxygen, and glass always contains some paramagnetic impurities. Therefore the tubes themselves must be carefully calibrated, and the volume of the displaced air must be accounted for. This is due to the 100-fold greater susceptibility of paramagnetic versus diamagnetic substances. It is possible to ascribe paramagnetism to a diamagnetic substance if these corrections are not made! Diamagnetic susceptibility correction We will use exclusively the molar susceptibility, M [cm3 mol-1], which is related to gram susceptibility (i.e. specific susceptibility) g [cm3g-1] by the molar mass. The gram susceptibility is related to V [dimensionless] by the density. M = g M g = V/ As stated above, M is negative if the substance is paramagnetic, and positive if it is diamagnetic. Since the unpaired electrons in a metal complex are usually only due to a few electrons in a large molecule, the sum of all the diamagnetic effects can be substantial. Fortunately the diamagnetic contribution is additive, so that the paramagnetic term paraM can be extracted according to the following formula: totalM = paraM + diaM(metal core electrons) + diaM(ligands) + diaM(ions) + diaM(solvate) Diamagnetic correction terms are tabulated in several textbooks (for example reference 1, p. 403). Pay careful attention to the units, which may be cgs or SI, and the two are not interchangeable. Microscopic theory of paramagnetism For a substance consisting of non-interacting paramagnetic centers (a condition which coordination compounds approximate much better than most other magnetic materials due to the insulating effect of the surrounding ligands), the magnetic susceptibility varies with temperature according to the Curie Law: M = C/T where C is the Curie constant. With increasing temperature, the magnetic moments (electrons) will move more randomly, lowering the paramagnetic contribution. In comparison, diamagnetism does not exhibit any temperature dependence. For substances which follow the Curie law closely, the effective magnetic moment is given by:

eff

para eff = 2.84 ( M T)

para 3k M T = N 2 A

1/ 2

1/ 2

Here is the Bohr magneton ( =

eh = 9.274 10-24 J T-1), k is the Boltzmann constant and 2 mc NA is Avogadro's number. Substituting the constants gives the second term, which gives eff in units of Bohr magnetons when paraM is expressed in cgs units.

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Part II Ligand Field Theory

Experiment 6

In a complex, the electric field of the ligands (the ligand field) usually quenches the orbital contribution to the paramagnetism. Therefore, we can make the assumption that only the spin angular momentum of the electron, and not its orbital angular momentum, contributes to paraM. Then the number of unpaired electrons, n, may be calculated from the equation, with given in Bohr magneton : = 2 {S(S + 1)} Since S represents the spin quantum number, and each electron has a value of , we can rewrite the first equation in terms of the total number of unpaired electrons: = {n(n + 2)} Thus the approximate value of the magnetic moment of any transition metal immediately gives us the total number of unpaired electrons. There are some important deviations from this simplified theory. Materials whose magnetic moments are not so well insulated from one another often follow a modified temperature dependence called the Curie-Weiss Law. Also many metal complexes have appreciable orbital angular momentum contributions to the magnetic moment. References 2 (simplified), 3 and 6 (detailed) address this more complex behaviour. Instructional goals: Properties of the following elements are highlighted: Fe, Ni, N and O. (1) (2) (3) (4) Experience with the synthesis of some classical coordination complexes of the transition elements. Learning the Gouy method of measuring bulk magnetic susceptibility. Experience with the calculation of effective magnetic moments of transition metal complexes from measured susceptibilities. The use of measured magnetic moments in determining the electronic structure of metal complexes and in distinguishing between high- and low-spin environments.

Pre-lab exercise 1. 2. 3. Write balanced equations for synthetic procedure (1) and (2). Assign the point groups of the complex ions in Figure 6-2. What is meant by strong- and weak-field ligands? What relationships do they bear to high- and low-spin environments? Illustrate with the materials studied in this experiment. In other words, what magnetic moments would you expect for the compounds studied in this lab? Why must care be taken not to wipe the Gouy sample tubes? Map out the timing of your afternoons work. Use free gaps of time to do other operations. Be realistic in the time allotted for each operation!

4. 5.

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Part II Ligand Field Theory Procedure Part 1: Preparation of tris(acetylacetonato)iron(III)

Experiment 6

Dissolve 5.0 g of ferric sulfate in 95 mL of distilled water. In this solution, dissolve 5.0 g of sodium acetate and immediately add to it, with stirring, a solution of 5 mL acetylacetone in 10 mL of ethanol. Filter the red product by Bchner filter and air dry it for 5 minutes. To recrystallize the product, dissolve it in the minimum amount of boiling ethylacetate, then add enough 95% ethanol to the hot solution until it is cloudy. CAUTION: there may be a lot of insoluble material which is not soluble; if so do a hot filtration through fluted filter paper, or simply decant the solution carefully. Avoid an excess of solvent! Cool to R.T. and afterwards put the flask on ice. Filter the red product and allow to air dry for 5 minutes. Part 2: Preparation of tris(ethylenediamine)nickel(II) thiosulfate In a fume hood dissolve 4.2 g of ethylenediamine and 4.4 g of nickel nitrate in 12 mL of water. Also, prepare a solution of 4.6 g of sodium thiosulfate in 50 mL of water. Heat the two solutions to boiling and mix them continue heating the mixture for 2-3 minutes, then cool the solution in cold water with constant stirring. Collect the product by Bchner filtration and wash it with cold water and dry it at 100C for about half an hour. Characterization Measure the melting point of both products. Calculate the percent yields and obtain their IR spectra as mulls. Compare the data with literature values. Magnetic measurements (1) (2) (3) (4) Measure the magnetic susceptibility of the following compounds using the Gouy balance: K3[Fe(CN)6] (provided) [Fe(acac)3] (procedure 1) K2[Ni(CN)4]H2O (provided) [Ni(en)3]S2O3 (procedure 2)

The tubes consist of 12 cm flat-bottomed Pyrex glass with an i.d. of ~4 mm. Note that these tubes are numbered. Each tube must be individually calibrated, so try to use a single tube for all your work. The tube can be cleaned with soap and water (use of a fine pipe-cleaner is recommended if stubborn deposits persist.) Rinse with distilled water and acetone, then dry in the oven. Do not wipe the tube dry, or wipe it clean afterwards. Always fill the tubes exactly and with a flat profile to the line marked on the glass about 2 cm from the top.

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Part II Ligand Field Theory

Experiment 6

Operation of the Gouy Balance Power Supply

(1) Before starting (i) Turn water to magnet on (tap located behind AA instrument) to a steady trickle. (ii) Ensure that current control on UPPER control unit is set to zero. Do NOT adjust the current control pot located on LOWER unit at any time! (iii) Turn POWER to ON on BOTH control units. Making measurements at full magnetic field (i) Turn current control knob on UPPER unit slowly up until needle on LOWER unit stabilizes dead centre on the REGULATION dial. (ii) The ammeter on the upper unit should read about 7 A. (iii) Make measurement. (iv) Turn current control knob back to zero to cut power to the magnet. Do NOT switch power off on the consoles until you are all done. At end of experiment (i) When all measurements have been taken, ensure the current control knob is set back to zero. (ii) ONLY when the current reads zero on the dial at upper left can the power to both control units be safely switched off.

(2)

(3)

Weigh the empty tube on the chain with field off (i.e. power to the electromagnet switched off). Then weigh the empty tube on the chain with the field on. It is necessary to maintain the same magnetic field for all measurements when the field is on. This requires a constant current flow. The current will decrease as the coils begin to heat (even with water cooling) so the current will have to be adjusted frequently. On our instrument, this is done automatically be a current regulator. Best results will be obtained if the electromagnet is left on in stand-by mode throughout the lab period. To correct for the diamagnetism of air, the volume of air must be determined. So weigh the tube filled with water on the chain, with field off. From the weight, knowing the density of water at the temperature of measurement, the volume V can be found. The volume susceptibility of air is 0.029 10-6 per mL. To determine the calibration constant for the apparatus, the dry tube is filled to the line with solid HgCo(SCN)4 as a standard. This blue solid should be a very fine free-flowing solid, but can be further pulverized with an agate mortar and pestle if necessary. Note: large errors can be made by inhomogeneously packed sample tubes. To minimize the problem, the following procedure is recommended. Introduce small portions of the finely powdered sample into the tube (2mm at a time) and pack by tapping firmly on a hard surface (not glass). If done properly, filling a tube will take 20 to 30 minutes. Weigh the tube with magnet off and on using the same current as before. Measure the temperature between the poles. HgCo(SCN)4 has a standard = 16.44 10-6 cm3 mol-1 (cgs units) at 20C, with a temperature dependence over the range 10C of 0.05 10-6 cgs units per degree. After making the measurement, return the HgCo(SCN)4 to its container so long as it has not been contaminated. If it is necessary to dispose some of this compound, do so in a mercury waste jar. Repeat the same measurements for the unknown sample. The measurements in summary are: Chemistry 3820 Laboratory Manual Page6-7

Part II Ligand Field Theory Current Temperature of water, Temperature between magnet poles, C: W1 Weight of empty tube, field off W2 Weight of empty tube, field on W3 Weight of tube filled, field off W4 Weight of tube filled, field on W5 Weight of tube filled with water (once only)

Experiment 6 __________A _________C _________C __________g __________g __________g __________g __________g

For each determination, repeat the measurements (as you proceed through the table) until W2-W1 and W4-W3 give constant values (0.05 mg) are obtained. The weights recorded are used as follows: V = (W5-W1) where is the density of water in g mL-1 at T = W2-W1 = W4-W3 m = W3-W1 In the equation: (g m) - (0.029 10-6) V = ( - ) Here is the calibration standard of the tube & magnet assembly at a certain field current. This gives the susceptibility g per gram of sample, where m is the mass in grams, is the correction for the diamagnetism of air and is the magnetic susceptibility of the actual sample under experimental conditions. Once the mass susceptibility is determined for the unknown sample, M = g M can be calculated from the known chemical formula. Then apply the diamagnetic correction and extract paraM, the molar paramagnetic susceptibility of the unknown. Report Hand in your product as well as all original spectra. Account for the values of eff you have obtained for all four complexes. Compare the two iron complexes with each other, and the two nickel complexes with each other. Discuss them in terms of the environment of the metal ion in each particular complex, the ligand field splitting of the d orbitals expected in that environment, and the variation in crystal field splitting which occurs as the ligands are changed. Your Discussion should address at least the following points: 1. What properties of HgCo(SCN)4 make it particularly useful as a calibrant for magnetochemical measurements? 2. Compare your effective magnetic moment results with data in the references provided. Comment briefly on the likely sources of error in the measurements you made. 3. Comment on the discrepancies between calculated and measured magnetic moments for the complexes you studied. 4. Could the method you have used to determine magnetic susceptibilities be used without adaptation to measure the susceptibility of a complex in solution? What problems might arise?

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Part II Ligand Field Theory

Experiment 6

References 1. 2. 3. 4. 5. Figgis, B.N.; Lewis, J. In Modern Coordination Chemistry: Principles and Mmethods, Lewis, J.; Wilkins, R.G. (Eds.); Interscience: New York, 1960, p. 400. [QD471.L62] Butler, I.S.; Harrod, J.F. Inorganic Chemistry; Benjamin/Cummings: Redwood City, Ca., 1989, p. 428ff. [QD151.2.B88] Dunn, T.M.; et al, Some Aspects of Crystal Field Theory; Harper & Row: New York, 1965, p. 58ff. [QD475.D8] Figgis, B. N. Introduction to Ligand Fields; Interscience Publishers: New York,1966. [QD471.F57] Wilkinson, G.; Gillard, R.D.; McClevery, J.A. Comprehensive Coordination Chemistry; Pergamon Press: Oxford, 1987, Vol. 1, pages 256ff and 271ff. (An up-to-date article on ligand field theory by B.N. Figgis with applications to magnetochemistry. Quite complex, but very readable account, with a good compilation of up-to-date information.) See also the individual articles on each element in this comprehensive series. [QD474.C65]

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