Inorganic Chemistry Year 3

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LABORATORY MANUAL INORGANIC CHEMISTRY III

Inorganic Chemistry Year 3

CONTENTS EXPERIMENT 1: ISOMERISM AND KINETICS IN COORDINATION CHEMISTRY 2 THE PREPARATION AND CHARACTERIZATION OF MESITYLENETRICARBONYLMOLYBDENUM(0) 3 4 MAGNETIC SUSCEPTIBILITY THE PREPARATION AND ESR STUDIES OF BIS(ACETYLACETONATO) OXOVANADIUM(1V) AND ITS PYRIDINE ADDUCT. ELECTRONIC SPECTRA OF NICKEL(11) COMPLEXES (a d8 SYSTEM) THE EFFECT OF SYMMETRY ON THE INFRARED SPECTRUM OF THE SULPHATE GROUP. 8 18 5 3

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EXPERIMENT 1:

ISOMERISM AND KINETICS IN COORDINATION CHEMISTRY

INTRODUCTION The purpose of this experiment is to prepare and study the kinetics of the interconversion of some of the isomers of a typical coordination compound. Historically, isomerism has played a central role in establishing the basic concepts of coordination chemistry upon which so much of modern inorganic chemistry is based. On the other hand, the reaction kinetics of coordination compounds is an area of continuing intense research activity. Much of the present interest in the mechanisms of the reactions of coordination compounds stems from their relevance to enzyme reactions where the active site frequently involves coordination to a metal ion. The first part of this experiment involves the preparation of the cis and trans isomers of dichlorobis(ethylenediamine)cobalt(III) chloride while in the second part the rate of conversion of the racemic cis isomer to the trans isomer is followed spectrophotometrically. EXPERIMENTAL (a) Preparation of Trans-Dichlorobis(ethylenediamine)cobalt(III) chloride. To a solution of 16 g of cobalt(II) chloride hexahydrate in 50 cm of water, contained in a 250 cm Erlenmeyer (or conical) flask, add with stirring 60 g of a 10% solution of ethylenediamine. A vigorous stream of air is drawn through the solution for 1-2 hours and then 35 cm of concentrated hydrochloric acid is added and the solution evaporated on a steam bath until a crust forms over the surface ( ca. 75 cm ). The solution is allowed to cool and stand overnight before the bright green plates of the hydrochloride, trans-[Coen2CI2]CI.HCI are filtered. These are then washed with alcohol and ether and dried at 110oC . At this temperature the hydrogen chloride is lost and the crystals crumbled to a dull green powder. Yield expected is ca. 8 g. (50 % based on ethylenediamine used). (b) Preparation of the cis isomer. A solution of the trans form yields the less soluble cis form on evaporation to dryness over a steam bath. The evaporation may need to be repeated but not more than three times (further repetition of the evaporation causes substantial decomposition) to effect cis formation. Finally unchanged trans form may be washed out with a little cold water. 3

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(c) The cis to trans isomerization. In methanol solution the purple cis form is isomerized to the (thermodynamically) more stable green trans form. In order to follow the reaction by spectrophotometry, it is necessary to record the spectra of both the cis and the trans isomer separately. To save time the following procedure is adopted. Prepare a solution (0.02M; 14 mg in 25 cm) of the trans isomer in methanol and record its UV-visible spectrum. Repeat this procedure for the cis isomer, recording the UV spectrum immediately after the solution has been prepared; then quickly place the solution, tightly stoppered, into a constant temperature bath at 35. Meanwhile from an examination of the spectra (discuss with your Demonstrator) select the most appropriate wavelength to follow the reaction. Measure the optical density D at this wavelength at 15 minutes intervals for about 90 min. by withdrawing samples from the thermostated solution. D may be measured by allowing the mixture to stand overnight. The isomerization reaction is first order. Then ln{cis} = -kt + c. it is easily shown that ln (D-D) = -kt + C' so that a plot of log (D-D) against time should give a straight line of slope k/2.303. (Note that since the reaction is first order neither the extinction coefficient for the two isomers nor the initial concentration of the cis isomer need be known). From your results, determine k and the half-life for the reaction. REFERENCE: 1. Journal of Chem. Ed. , 1962, 39, 634. 2. J.C.S. 1953, 2696.

Inorganic Chemistry Year 3

EXPERIMENT 2: THE PREPARATION AND CHARACTERIZATION OF MESITYLENETRICARBONYLMOLYBDENUM(0) INTRODUCTION Isolated organometallic compounds of the transition elements have been known for a long time (e.g. Zeizes salt 1827). However, it was not until the 1950s, following the accidental discovery of ferrocene, that the organometallic chemistry of the transition metals became a major area of inorganic research. Perhaps the most versatile starting materials for the laboratory synthesis of transition metal organometallic compound are the metal carbonyls. In this experiment molybdenum hexacarbonyl is reacted directly with an organic aromatic (mesitylene). In general, the reaction can be represented as: Ar + Mo(CO)6 EXPERIMENTAL (a) Preparation NOTE: THIS PREPARATION MUST BE PERFORMED IN A FUME HOOD. METAL CARBONYLS ARE VERY TOXIC. Assemble the apparatus as shown in the diagram using a 50 cm3 round bottom flask and a simple reflux condenser (water need not be circulated through the condenser: air cooling is sufficient). Add 1.8 g Mo(CO)6 to the flask followed by 10 cm3 of mesitylene and 10 cm3 decalin. Flush the apparatus with a moderate stream of nitrogen for about 5 min. After the nitrogen flow is turned off and the stopcock closed, bring the mixture to a moderate boil with the heating mantle. Reflux for 2-3 hr (yield improves with stirring), then turn off the heat and immediately flush with nitrogen. This facilitates the removal of unreacted Mo(CO)6 from the solution and also prevents the mineral oil in the bubbler from being sucked back into the reaction vessel. Allow the mixture to cool to room temperature, then filter on a medium frit (aspirator pump). For purification, the crude product is dissolved in the minimum amount of hot CH2Cl2 (FUME CUPBOARD), 5 ArMo(CO)3 + 3CO

Inorganic Chemistry Year 3

filtered hot (medium frit*, aspirator pump) and then allowed to cool. The resulting lemon coloured crystals are collected and dried on a frit. If necessary, additional product can be obtained by reducing the volume of the mother liquor. Further purification of the recrystallized product may be achieved by vacuum sublimation (100C, high vacuum). (b) Characterization. 1. IR Spectrum. Record the IR spectrum of the product as a nujol mull over the whole range and assign the important bands. Also record the IR spectrum of the compound in solution in CHCl3 in the region 1800-2000 cm-1. Comment on the differences between the two spectra in this region. 2. NMR Spectrum. Prepare 0.5 cm3 of a saturated solution of the product in the specially purified CHCI3 (obtainable from the Laboratory Assistant) and record the NMR spectrum. Comment on the spectrum particularly the information it provides about the structure and bonding of the complex. Explain why free mesitylene shows two peaks at 2.25 and 6.78 ppm (vs. TMS in CDCI3 of relative intensity 9:3). 3. Mass Spectrum A copy of the mass spectrum is given in Appendix 2A. Use it to verify the molecular weight of the compound. Comment briefly on the spectrum (molybdenum has seven naturally occurring isotopes ranging from 9 to 24% abundance). QUESTIONS 1. Use the spectral data to determine the structure of the complex? 2. To what symmetry group does the complex belong? 3. What would an ESR spectrum of this compound reveal? REFERENCES 1. G. E. Coates, M. L. H. Green and K. Wade: Organometallic Compounds Vol. 11. (The Transition Elements) 1968. 2. B. Nicholls and M. C. Whiting, J.Chem. Soc., (1959) 551. 3. F. A. Cotton and Wilkinson, Advanced Inorganic Chemistry. 4. R. J. Angelici, J. Chem. Ed., 45 (1968) 119. 6

Inorganic Chemistry Year 3

Inorganic Chemistry Year 3

EXPERIMENT 3 MAGNETIC SUSCEPTIBILITY Introduction The aim of the experiment is (1) to acquaint the student with two of the experimental techniques involved in magnetochemical measurements, viz, the Gouy method for solids and the Evans method for solutions, and (2) to examine the magnetic behaviour of a complex in the solid and solution state, and to gain information about stereochemical changes if any. (The student may perform either PART A or PART B) PART A Preparation To a stirred solution of 3.9 g of manganese chloride (MnCl2.4H2O) and 10.2 g of sodium acetate (CH3COONa.3H2O) in water (150 cm3) add slowly acetylacetone (18.8 cm3). Follow by adding slowly, with stiring, a solution of potassium permanganate (0.79 g in 38 cm3 of water) and a few minutes later in small amounts, a solution of sodium acetate trihydrate (9.8 g in 40 cm3 of water). Heat on a water bath for 20 minutes at about 60, cool in ice-cold water and filter off the dark solid. Wash the product with ice-cold water, and dry in a vacuum desiccator over anhydrous calcium sulphate. Dissolve the dry chelate in warm toluene (20 cm3), filter and reprecipitate the complex by cooling and adding petroleum ether (40-60) (about 75 ml). Dry in a vaccum desiccator. Calculate the percentage yield. Analysis The analysis of manganese is particularly convenient to carry out spectrophotometrically as permanganate ion. Make up a solution of 100 mg precisely of potassium permanganate in 1 litre of distilled water. Then by dilution, make up solutions containing 1, 2, 3 and 4 mg of permanganate per 100 cm3. Measure the absorbance of these solutions in a 1-cm cell at 528 nm on the UV-visible spectrophotometer , and plot a graph of absorbance vs. concentration. Weigh out accurately about 100 mg of the manganese(III) acetylacetonate and dissolve it in 50 cm3 of nitric acid which contains 12 cm3 of concentrated acid for 5 minutes, cool, add about 0.5 g. of A.R. sodium bismuthate and boil again for 5 minutes. At this stage the solution 8 A study of manganese(III) acetylacetonate.

Inorganic Chemistry Year 3

should be purple and/or manganese oxides should have precipitated. If this has not occurred, add a further 0.5 g. of sodium bismuthate and boil again for 5 minutes. Very slowly add aqueous concentrated sodium sulphite with stirring until the solution clears. Boil until all oxides of nitrogen are expelled, cool to 15C and add sodium bismuthate in small quantities with stirring until no further colour changes takes place (about 0.5 g. of sodium bismuthate) and stir. Add 50 cm3 of the 3 in 100 dilute nitric acid and filter through a sintered glass crucible. Wash the reaction flask and the sinter with the dilute nitric acid until filtrate becomes colourless. Dilute the purple filtrate and washing to exactly 1 litre. Measure the absorbance of this solution at 528 nm, then dilute 50 cm3 of the solution to 100 cm3 with distilled water and repeat the absorbance measurement on the diluted solution. Using the previously prepared graph determine the percentage manganese in the manganese(III) acetylacetonate. Magnetic Study (a) Measure the paramagnetic susceptibility of the complex as a solid (see Appendix 3A, p. 3-9) (b) Run the NMR spectrum of a CHCl3 solution containing a known concentration of the complex (ca. 0.01g/ml). Insert a capillary tube containing pure CHCl3 as external reference (see Appendix 3B). From the frequency separation of the proton resonance in the CHCl3, solution relative to the external reference of pure CHCl3, calculate the magnetic susceptibility of the complex in solution.

Inorganic Chemistry Year 3

PART B Structural Equilibrium in a Schiff-base complex of Ni(II). In this experiment, we study the equilibrium between squareplanar and tetrahedral stereoisomers of a bis(alkylsalicylaldiminato) nickel(II) complex in solution. Preparation of bis(isopropylsalicylaldiminato)Nikel(II) In a FUME HOOD add 7.0 cm3 (0.08 mol) of neat isopropylamine to 4.2 cm3 (0.04 mol) of salicylaldehyde dissolve in 50 cm3 of methyl alcohol contained in a 250 cm3 beaker. (Take care as the amine is volatile and has a pungent odour). Allow the mixture to stand for 5-10 minutes at room temperature covered with a watch-glass. Then add to the mixture a solution of 5.0 g. (0.02 mol) of nickel(II) acetate tetrahydrate dissolved in 70 cm3 of distilled water VERY SLOWLY AND STIR CONTINUOUSLY. When the addition is complete, add a solution of 5.2 g (0.04 mol) of sodium acetate tri-hydrate in 50 cm3 of water. At this stage a light-green suspension forms. This is an intermediate which is gradually replaced by the darker green product complex. Heat the suspension at 50C with continuous stirring for 10-20 minutes or until flocculation occurs. DO THIS IN THE FUME HOOD, and DO NOT HEAT ABOVE 55C. Cool the beaker and its contents in water to room temperature, stirring the suspension during cooling. Filter this darker green precipitate through a Buchner funnel, and wash it on the filter with several portions (3 x 20 cm3) of water. When washing the precipitate with water and also in the subsequent washing with ethanol, mix the precipitate thoroughly using a glass rod during each washing. Wash the precipitate with 15-20 cm3 of ethanol, then suck dry on the filter for 10 minutes. DRY THE PRECIPITATE THOROUGHLY BEFORE PROCEEDING ON TO THE RECRYSTALLIZATION STEP. Recrystallize the product from chloroform in the following manner: IN THE FUME HOOD, add 50 cm3 of chloroform to the complex contained in a 100 cm3 round bottom flask and add some boiling chips. Place a reflux condenser on the flask and boil the mixture for about 5 minutes or until almost all of the solid has dissolved. (The flask containing the chloroform should be heated over a water-bath in the fume hood). Filter the hot solution through a pre-heated Buchner funnel, and place the filtrate into an evaporating dish and slowly evaporating the solvent until about 10-15 cm3 remain. (This can be done on a hot-plate in the fume hood). Filter off the dark-green crystalline solid and wash it with 2 x 5 cm3 portions of ether, then suck dry on the filter. Store the solid in a desiccator over silica-gel, and record the yield of dry product. Calculate the percentage yield on the basic of nickel acetate used.

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Magnetic Study (a) Measure the magnetic susceptibility of the solid by the Gouy method (see Appendix 3A, p. 3-9). (b) Obtain NMR spectra of an approximately 0.05M solution of the complex in each of the solvent mixture* specified below. The solution is prepared by dissolving an accurately weighed sample in each of the solvent mixture in a 10 cm3 volumetric flask:i) ii) 10% toluene + 90% benzene (By volume. Prepared by mixing 10 cm3 of toluene with 90 cm3 of benzene). 10% toluene + 10% pyridine + 80% benzene (By volume. Prepared by mixing 10 cm3 of toluene, 10 cm3 of pyridine and 80 cm3 benzene).

NOTE: NMR spectra of these solvent mixture are provided. See Appendix 3C for the calculation of the mass susceptibility o of these solvent mixtures. Diamagnetic correction of solvent: The frequency separation for the methyl resonance in the solvent mixture relative to the pure toluene capillary is a measure of the solvent susceptibility, hence this frequency shift is equivalent to a diamagnetic correction and must therefore be subtracted from the overall frequency separation measured for the metal complex. From the corrected frequency separation calculate g, M, Mcorr (corrected for the diamagnetism of the ligands. See Appendix 3D), and hence the solution Bohr Magneton Number, eff. (see Appendix 3B). QUESTIONS (All students are to attempt Q.1 and Q.2 Q.3 Q.6 refer to PART B)

1. The Spin-only formula for calculating magnetic moments is given in Appendix 3A. Under what conditions is it applicable? Why does it break down sometimes? (See Cotton and Wilkinson and Ref. 3 and 4). 2. What conditions should be satisfied by a complex whose magnetic susceptibility we wish to determine in solution? Are these any restrictions to the type of reference solvent we could use? (See Ref. 4, 5 and 6). On the basis of your answer, discuss the feasibility of determining eff for the following:(a) Fe(CN)63- in aqueous solution using the tert-butanol methyl resonance as reference. 11

Inorganic Chemistry Year 3

(b) CuCl42- in pyridine using the toluene methyl resonance as reference. (c) Ni(DMG)2 in benzene using the methyl resonance of 4methylpyridine as reference.(DMG = dimethylglyoxime). 3. Explain the change in magnetic behaviour of the Ni(salen)2 complex on going from the solid to solution. 4. Is there any difference in magnetic behaviour on going from toluene/benzene mixed solvent to pyridine/toluene/benzene mixed solvent? Suggest a possible explanation for your observations. 5. What is the generalized structural formula for a Schiff base(salicylaldimine) ligand and how are they synthesized? What is/are the usual structure(s) adopted by metal complexes containing such ligands? (See Ref. 1 and 2) 6. Assuming that in toluene/benzene, an equilibrium exists between square planar and tetrahedral forms, Nisq K NiTd

Calculate the equilibrium constant K from the magnetic data. (See Appendix 3E). REFERENCES 1. R. H. Holm and M. O Connor, Prog. in Inorg. Chem., 14, 338-342 (1971) 2. R. H. Holm and K. Swaminathan, Inorg. Chem., 2, 181 (1963) 3. B. N. Figgis and J. Lewis, Modern Coordination Chemistry , Ed. By J. Lewis and R. G Wilkins, Interscience, (1960), Ch.6. 4. B. N. Figgis and J. Lewis, Technique of Inorganic Chemistry, 4, 137 (1965), Ed. By H. B. Jonassen and Q. Weissberger, Interscience. 5. D. F. Evans, J. Chem. Soc., 2003 (1959). 6. T. H. Crawford and J. Swanson, J. Swanson, J. Chem. Ed., 48, 382 (1971). 7. P. W. Selwood, Magnetochemistry, Interscience, John Wiley & Sons, New York, 1956, Chapter 8.

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APPENDIX 3A
THE MEASUREMENT OF MAGNETIC SUSCEPTIBILITY

THEORY AND DEFINITIONS

Magnetic susceptibility is defined as the ratio of the intensity of magnetism induced in a substance to the magnetising force or intensity of field to which it is subjected. It provides important electronic structural information of the transition and rare earth metal complexes. Traditionally, measurement of magnetic susceptibility has been made using the Gouy and the Faraday methods. The original instruments were originally made from conventional laboratory balances and large permanent magnets. The magnets were brought towards the sample and the positive or negative change of apparent weight was noted. The balances and sample holder were free of ferromagnetic materials. The systems that evolved were very large relying on heavy magnets, fixed in position, and a moving sample. The late Professor Evans of Imperial College London introduced an innovative step to the measurement. Instead of measuring the apparent weight loss or gain of a suspended sample, the force acting upon a suspended magnet was detected, thereby turning the method on its head. The advantage realised by this step led to the development of the light and inexpensive magnetic susceptibility balance, which is the MSB-MKI. The model used in our laboratory is MSB-AUTO which has many improved features and which still relies on the advantage first obtained by Professor Evans. The three most common ways that magnetic susceptibility values are expressed are with reference to the volume of sample, the weight of sample, and the moles of sample. These terms are commonly referred to as volume susceptibility, mass susceptibility, and molar susceptibility. The equations relating these terms are provided below: VOLUME SUSCEPTIBILITY The volume susceptibility, designated , is expressed by the following formula: = I H

where I is the intensity of magnetism included in the substance and H is the intensity of the applied external magnetic field The volume susceptibility can be quite variable due to changes in the density of the substance, particularly when the sample is a gas or solid. The mass susceptibility, g, introduces a density factor in the following manner: MASS SUSCEPTIBILITY g = d

where d is the density of the substance

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Note that g has units of reciprocal density,

cm3 g

MOLAR SUSCEPTIBILITY The most common way of reporting a magnetic susceptibility value in the literature is by molar susceptibility, designated as M. The relationship of molar susceptibility to mass susceptibility is shown below: M = g x MW where MW is the molecular weight of the substance. The M is the best value to use when comparing different materials qualitatively or assessing the potential of a quantitative applications since the value of the term is not subjected to variations due to the method of measurement or to sample density. Since the Auto, like other methods, measures Volume Susceptibility and the literature is quoted in Molar Susceptibility, the conversion between the two values is quite common in magneto chemical studies. The initial step in the conversion, that is obtaining a g value from , is done within the Auto provided the length and weight of the sample are known and can be entered into the unit.

Calculation of magnetic moment The molar susceptibility obtained has to be corrected for the inherent diamagnetic contribution (dia) from the ligands and metal ions using the table of Pascals constants. i.e. corr =
exp M - dia e

The relationship between molar susceptibility and effective magnetic moment , eff is eff = 2.84 corr T Bohr Magneton

It can also be shown that the effective magnetic moment, eff is given by, eff = n(n+2) B.M. [Note : A system obeying Curie law would have no or negligible orbital contribution towards the magnetic moment]. For the details on the operation of the MSB-AUTO magnetobalance, please refer to the operating manual. Cleaning and Storage of Sample Tubes [Note : The sample tube used in this magnetobalance is a high precision tube made of silica. It is expensive and should be treated with care!]

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The good maintenance of the sample tubes is essential for good result. Sample tubes can be cleaned with the conventional detergents and/or organic solvents, depending on the nature of their sample. In difficult cases, strong acids, viz. HCl or HNO3 may be required. Pipe cleaners have proven to be a useful tool. Similarly an aerosol can of ethylene dichloride, supplied with a plastic capillary spout (available for degreasing electronic components) has proven invaluable in removing oil from the tubes when analysing for wear metals. The tube should be stored in a dust free environment and its susceptibility should be measured before introducing a sample. As a final precaution, the outside of the tube should be wiped with a dust free wiper just prior to introducing it to the balance, particularly if it has been allowed to lay on the bench.

Packing Sample into the Tube The tube is packed as follows. The solid to be measured is ground to a fine powder in a mortar and pestle. HgCo(NCS)4 forms very fine crystals and can usually be used without grinding. Note that the greatest source of error in Gouy measurements is in homogeneous packing. It is essential that an effective routine for the packing of the powder into the tube is developed and adhered to. Good packing requires time and patience. A small amount of the compound is picked up from the mortar, placed in the flares mouth of the tube, and tapped to the bottom of the tube. The closed end of the tube is tapped for about a minute on two sheets of filter paper on a wooden bench. (See a demonstrator about this). This process is continued until the tube is filled to the mark - make sure that the sample does not pack down with further tapping. Wipe away any excess compound from the mouth of the tube to remove excess moisture. Standard to calibrate the balance Several standards can be used for checking the calibration of the balance. Perhaps one of the most reliable trouble free standard is water (106 g = -0.720), since it is readily available in pure form. A singly distilled water sample should suffice. HgCo(SCN)4 (105 g = +1.644 at 20oC) is considered one of the best solid standsrds. At other temperature, use the relation dg d = -0.05 x 10-6 cgs/K

to obtain the exact g value. The ethylenediamine salts of nickel, Ni (en)3 S2O3 (105 g = +1.104) is also a useful secondary standard. Many solid samples of paramagnetic substances, if properly dried and ground and packed, usually give within 2% of their literature value. If it is necessary to recalibrate, please refer to Section 5.2 of the original operators manual.

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APPENDIX 3B EVANS' METHOD FOR MAGNETIC SUSCEPTIBILITIES

(Extracted from J. Chem. Ed., 46, 1969, 167)

This method is based on the principle that the position of a given proton resonance iin the spectrum of a molecule is dependent on the bulk susceptibility of the medium in which the molecule is found. The shift of a proton resonance line of an inert substance due to the presence of paramagnetic ions is given by the theoretical expressions5 o 2 3 ') ( - _

(1)

where is the shift, o is the applied field, v is he volume susceptibility of the solution containing paramagnetic ions, and is the volume susceptibility of the reference solution. For example, if an aqueous solution of paramagnetic substance with 3% of t-butylalcohol as an inert reference substance is placed in the inner tube of a concentric cell, and an identical solution without the paramagnetic substance is placed in the annular section of the cell, two resonance lines will usually be obtained for the methyl protons of the t-butyl alcohol due to the difference in the volume susceptibilities of the solutions. This is in accord with eqn. (1). The gram susceptibility, g of the dissolved substance is given by the expression5. g = 3 2om do - ds + o + o () m

(2)

where is the frequency separation between the two lines in cycles/sec, o is the frequency at which the proton resonances are being studied in cycles/sec, m is the mass of substance contained in 1 ml of solution, o is the mass (gram) susceptibility of the solvent (-0.72 x 10-6 cc g-1 for dilute t-butyl alcohol solutions), do is the density of the solvent, and ds that of the solution. For highly paramagnetic substances, the last term can often be neglected5. The molar susceptibility, the effective magnetic moment and the "spin only" number of unpaired electrons may be calculated by the same procedure used for the Gouy measurements (See Appendix 3A). (SEE REFERENCES 5, 7 AND 8).

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APPENDIX 3C MASS SUSCEPTIBIILITY OF SOLVENT MIXTURES

For a mixture of non-interacting components, Mass susceptibility, o = mf(i). o '. i mi where mf = which is the mass fraction of the i-th component mi i Use of this equation and the table below would enable us to calculate the mass susceptibility of the solvent mixtures used in this experiment.

TABLE SOLVENT Benzene Toluene Pyridine Chloroform MASS SUSCEPTIBILITY o x 10-6 (c.g.s. or Gaussian units) -0.702 -0.7176 -0.622 -0.497 DENSITY g cm-3 0.876 0.863 0.981

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APPENDIX 3D DIAMAGNETIC CORRECTIONS

When making diamagnetic corrections, an addition to the measured value is made for each atom present in the molecule. The relevant diamagnetic susceptibilities are given in the table below:-

TABLE DIAMAGNETIC CORRECTIONS (c.g.s. units) (All values x 10-6/g atom Element/Ion H C C (aromatic) O (alcohol) O (carbonyl) N (C=N) Mn3+ Ni2+ -2.93 -6.00 6.24 -4.61 +1.73 -5.57 -10.0 -12.8

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APPENDIX 3E
Consider at equilibrium we have n mol of each of the square planar and tetrahedral forms present, each with a MOLAR magnetic susceptibility of M, then for the equilibrium: NiSq K = We can write, nsq obs = . Msq + n But, since Mobs = 0, then, nTd . d n

NiTd

nTd nSq

nTd Mobs = . MTd (nTd + nSq) Now, eff = 7.977 x 102 [ M (SI).T]1/2 i.e., eff2 = constant x M at a given temperature, thus we can write eff2(Td)

nTd eff2 = (nSq + nTd)

Assuming that the maximum Bohr Magneton Number, eff, for a tetrahedral [Ni(salen)2] complex in solution is about 3.3 (See Reference 1), it is then possible to obtain an expression for K which can be solved using the observed value for eff,(obs) which you calculate from your data.

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EXPERIMENT 4: THE PREPARATION AND ESR STUDIES OF BIS(ACETYLACETONATO) OXOVANADIUM(1V) AND ITS PYRIDINE ADDUCT. INTRODUCTION Electron Spin Resonance Spectroscopy (ESR) sometimes known as Electron Paramagnetic Resonance Spectroscopy (EPR) is a branch of spectroscopy in which radiation of microwave frequency is absorbed by molecules possessing electrons with unpaired spins. It is an important technique for the investigation of electronic and kinetic studies of systems which have a net electron angular momentum. These include free radicals, triplet state systems most transition-metal ions and point defects in solids. Free electrons (in the absence of a crystal field or magnetic field) are aligned in a random manner and in the presence of an external field they are ether aligned with the field (lower energy state) or in opposition with the field (higher energy state).

This is called the first order Zeeman effect. The difference in energy between the two states is proportional to the applied field (Fig. 1) E = geeHo where ge is spectroscopic splitting factor or simply the g-factor and equals to 2.0023 for a free electron. In quantum mechanical terms, the allowable spin states are quantized and the component Ms of the election spin vector can have values which are +s or s i.e. Ms = +() or Ms = - (). For a given applied field Ho (gauss) electron in a lower energy state Ms = - can be excited to a higher energy state Ms = + and the energy required for transition is given by E = h = geeHo (ergs)

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where is the frequency of the applied radiation (cps or Hz). In the absence of nuclear spin therefore we would expect an unpaired electron to give a line spectrum corresponding to a Ms = - Ms = + transition. Ms= E = geeHo Energy Ms = E=h=geeHo Ms = - E = - geeHo

Ho Applied field (Fig. 1)

In ESR spectroscopy, a magnetic field of around 3000 gauss is normally used and this brings the radiation frequency to lie in the microwave region of the electromagnetic spectrum (~ 9000 MHz). The nucleus also has associated with it a spin and the nuclear spin quantum number I may have values 0, , 1, 3/2, 2 etc. In the presence of a magnetic field the nuclear states are quantized and the component MI of the nuclear spin vector may have the following values 1, (1-1), (1-2).-1 This is the nuclear Zeeman effect and the energy required for the transition is given by E = h = gNNHo. (It is interesting to note that the energies required to effect a transition of an election is much higher than that of a nucleus. Thus the resonance frequency in ESR is about 700 times larger than for the NMR transitions). Hyperfine Splitting. When an unpaired electron comes in the vicinity of a nucleus with spin I, an interaction takes place which causes the absorption signal to be split into 2I+1 components. (e.g. three lines are expected for an unpaired electron on N where I = 1). This splitting results from an interaction between the nuclear spinelectron spin coupling and the energies of the levels are given by

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E = gHMS + AMSMI where A is referred to as the hyperfine coupling constant. Using the above equation and selection rules of ESR i.e. MI = 0 and MS = +1, the energies for each level and the energies of the four transitions for a system where S= and I= 3/2 (Fig. II) can be calculated. The difference in energies between each of the four transitions can also be calculated.
+3/2

geeHo

+ - - 3/2 -3/2 -

Ms= - geeHo

+ + 3/2

Fig. II Tetravalent vanadium is a d1 system and therefore possesses an electron spin of . The magnetic moment of this spin can interact with that generated by the nuclear moment of this spin can interact with that generated by the nuclear spin of V51 (I = 7/2) making it possible for it to be studied by ESR spectrometry. In fact ESR studies of the vanadyl VO2+ system have led to a clearer understanding of the structure and bonding of vanadium (IV) complexes. The number of hyperfine lines resulting from the interaction of the lone electron with nuclear spin of V51 is given by (2I + 1). The spectra of VO2+ systems in solvents of low dielectric constants are relatively simple and show eight well-defined lines, each separated by a hyperfine coupling constant Aiso of around 110 gauss. The value of Aiso is a direct measure of the density of the unpaired electron in the neighbourhood of the metal nucleus. Hence it is an important parameter in the discussion of bonding in the system. For example, most VO2+ complexes have the square pyramidal structure and are therefore capable of coordination with Lewis bases at the remaining vacant site. A decrease in the value of Aiso is attributable to an increase in the basicity of the coordinating molecules (because of greater delocalization of the unpaired electron).

EXPERIMENTAL

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Inorganic Chemistry Year 3

(a) Preparation of Bis(acetylacetonato)oxovanadium (IV), VO(acac)2. Reflex a solution of 2.5 g vanadium pentoxide in 6 cm3 water to which has been added 4.5 cm3 concentrated sulphuric acid and 12.5 cm3 ethanol. After 1-2 hours, the colour of the slurry changes from green to blue. Filter and add 6.5 cm3 acetylacetone to the solution. Neutralize the solution by adding slowly and with stirring a solution of 10 g anhydrous sodium carbonate in 60 cm3 water. Filter the product and dry in air. Recrystallize from a chloroform-ether mixture. Dissolve the product in a minimum of hot,dry chloroform, cool and add ether dropwise to complete the precipitation. (b) Preparation of Pyridine Adduct. *The operation below must be carried out in the fume cupboard. Dissolve a portion of the bis(acetylacetonato)oxovanadium(IV) already prepared in benzene and reflux for 30 minutes with a large excess of pyridine. Concentrate to a small volume by distilling off benzene and pyridine and crystals should form on cooling in ice. The addition of small amount of ether should improve the yield. Filter and dry in a desiccator. (c) Infrared spectra: Determine the infra-red absorption spectra of the complex and its adduct as outlined below and compare the two. The band occurring at 995 cm-1 in the spectrum of the complex has been identified as a V=O stretching mode. Determine the amount by which this band has shifted in the spectrum of the complex and suggest the reason for this shift. Are there any other differences between the two spectra? PREPARATION OF THE SAMPLE FOR RECORDING THE INFRA-RED SPECTRUM Make sure that the compound to be investigated has been thoroughly dried. Grind a small amount (about 10-20 mg) very finely with an agate mortar and pestle, add one drop of nujol (use a dropper for this purpose) and grind again. If necessary, add a second drop of nujol and regrind. Wipe the surface of the sodium chloride disc with a clean dry tissue, being careful not to touch the flat surface of the disc with your fingers. Do NOT under any circumstances allow the sodium chloride disc to become damp and see that it is not scratched. Carefully smear the nujol mull onto the surface of the disc and insert it into its holder. When the spectrum has been obtained, wipe off all traces of the mull from the disc with a clean and dry tissue. (d) Preparation of Sample for ESR Spectrum*

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Inorganic Chemistry Year 3

5 cm3 of a 0.05M solution of VO(acac)2 are prepared in redistilled toluene. It is necessary to flush the system with dry nitrogen. Introduce the sample to fill about 1 inch of the ESR quartz tubing as you would for running NMR spectra. Stopper the tubing and record the ESR spectrum at room temperature. The spectrum of VO(acac)2py is similar to that of VO(acac)2 and has a Aiso value of 105.3 g and g = 1.9699. Notice the separations between subsequent lines (Aiso) are not constant and have values ranging from 98.3 gauss at lower fields to 118 gauss at higher fields. This is mainly due to the fact that at weak fields the quantum numbers MS and MI are not pure. As a result there is a non-liner divergence of energy levels as the field increases. In the case of VO(acac)2, the hyperfine value is approximately equal to the spacing between the fifth line and the fourth line. i. e. h5 h4 = 108 gauss (refer to the attached spectrum). *NOTE: You need not carry out this procedure, but obtain a copy of the spectrum from your lecturer/lab. assistant. QUESTIONS 1. Using the selection rules for ESR, sketch the hyperfine energy levels diagram obtained from the interactions of the lone electron with V51 nucleus. 2. Assuming the hyperfine splittings to be symmetrical calculate the g value for VO(acac)2 (Bohr magneton B = 0.92731 x 10-20 erg/gauss). 3. the following stretching frequencies and Aiso values are observed for VO(hfac)2 and Vo(tfac)2. (V=O) (cm-1) VO(hfac)2 VO(tfac)2 1024 1010 Aiso(gauss) 112.6 110.1

Compare these values with those obtained for VO(acac)2 and discuss the results. (hfac = hexafluoroacetylacetonate; tfac = trifluoroacetylacetonate) 4. Comment on the Aiso and (V=O) values of VO(acac)2py relative to that of VO(acac)2. REFERENCES 1. R. S. Drago Physical Methods in Inorganic Chemistry (Reinhold) 2. J. P. Fackler and J. A. Smith, J. A. C. S. 92, 5787 (1970).

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Inorganic Chemistry Year 3

3. C. M. Guzy et al., J.Chem. Soc. (A), 2791 (1969) 4. V. Selbin et al., J. Inorg. Nucl. Chem., 25, 1359 (1963). 5. R. A. Rowe and M. M. Jones, Inorg. Synth. 5, 115, (1957)

EXPERIMENT 5: ELECTRONIC SPECTRA OF NICKEL(11) COMPLEXES 23

Inorganic Chemistry Year 3

(a d8 SYSTEM) Aim of experiment To construct the energy level diagram for nickel (11) (within the limits dictated by the various values of the ligands) from the spectra obtained for the series of complexes, and to use this to derive spectral and other information on nickel complexes in general. Introduction Because of the differing symmetry properties of dorbitals, their initial degeneracy is removed when they are brought under the influence of external fields other than a uniform spherically symmetric one. Similarly the Russell Saunders states associated with the various d orbital configurations are also split. In the case of d1 and d9 (by the hole formalism) this gives rise to the energy level diagram shown in Figure 1. d9 oct
2

T2

2/5
2

d1 oct

E -3/5
2

3/5 -2/5

E O

T2 Fig. 1

Other multi electron systems are more complicated because the interaction of several electrons gives rise to a series of Russell-Saunders states, G, F, P, G etc., which are affected differently by the Oh field. Thus for d2 and d8, we have the terms 3F,3P,1D,1G, and 1S, which are split by the ligand field as shown in Figure 2. When an electron undergoes a transition from the ground state to an excited state, the molecule must absorb energy. In the case of the d - d transitions the absorptions occur in the near UV, visible and the near IR. To a first approximation these transitions are forbidden, but more refined theory allows them to occur to give weak absorptions, as the Laporte rule is broken down. The spin selection rule may also be overcome, and when it is we observe very weak bands with an intensity of about 1/100 that observed for spin allowed transitions. For an octahedral nickel(11) complex, the following spin - -allowed absorptions are expected:-

24

Inorganic Chemistry Year 3

3

A2g

T2g

A2g

T1g(F)
d2 oct

A2g

T1g(P)

d8 oct 3T (P) 1 3T (F) 1 1T 2 3P

3A

3T (P) 1

3 /5

3T

1E

-1

/5

-6 3A _ 2

/5

3F

Fig. 2 Procedure Obtain samples of the complexes listed in Table 1 from the lab assistant (or if not available prepare a sample, see lecture/demonstrator in charge) and prepare solutions as described in the Table 1. Table 1: Solutions of complexes to be prepared. Complexa 1. [Ni(bipy)3]SO4.6H2O 2. [Ni(en)3]Cl2.2H2O 3. [Ni(NH3)6]CI2 4. [Ni(H2O)6]SO4 5. [Ni(DMSO)6](CIO4)2 6. K4[Ni(NCS)6]4H2O Solvent and Blank. Water 20% en Aqueous NH3 Water DMSO 10M KSCN in water Concentration 0.05M 0.05M 0.05M 0.05M 0.05M 0.05M

bipy = 2,2-bipyridyl ; en = ethylenediamine ; DMSO = dimethylsulphoxide.

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Inorganic Chemistry Year 3

Record the spectrum of each solution in the region 200 1100 nm. 1. Plot the energy diagram E versus based upon the ground state 3A2g as the energy zero for all values of (E and in units of cm-1) for the complexes 1- 6, Clearly labelling the various states (Note: The transition energy for the lowest energy absorption (3A2g 3T2g) for the d8 case gives the value of directly for the complex under investigation.) 2. Assume that the free ion 3F 3P separation is 15,836 cm-1 and that the energy of the 3A2g ground state varies according to E(3A2g) = - 6/5 Construct the Orgel diagram for nickel (II). 3. Answer the following questions: i) ii) Assign the 2 bands in the observed spectrum of complex 5, and estimate the frequency of the missing band. Estimate the frequency of the absorption maximum for the 3 A2g 3T1g(P) transition in complex 1. Why is it not possible to get this directly from the spectrum? (Do not include limitations of instrumentation as a valid reason). Predict the position of the absorption maxima for Ni(o phen)3SO4.9H2O and KNiF3 and with the aid of Figure 3 , deduce the colour of these compounds. Fig. 3 Near Infrared Red 13,300 Orange Yellow 15,400 17,000 Green Blue Violet Ultraviolet (1)

iii)

19,000 20,400 23,300 25,600cm-1

iv) Arrange the ligands in the spectrochemical series, that is in order of increasing . v) Calculate the extinction coefficients for complexes 1 -5. Comment on the differences, if any, between them and those of d d transitions in tetrahedral complexes, e. g. NiCl42- ( = 200) and for charge transfer transitions ( = 104 105) e.g. MnO4-. vi) Using equation 1, determine the mean energy (E) of the 3F state, relative to the 3A2g level, for complexes 1 6. For complex 6 use the diffuse reflectance data. Calculate the

26

Inorganic Chemistry Year 3

energy Eexp = (3T1g (P) E) for each complex. vii) Using Eexp calculated above, calculate P in the following equation for each complex. [3/5 P 4/25 2 ] + [ - 3/5 P ] Eexp + Eexp2 = 0 (2) This equation relates the energy of the 3T1g terms to the crystal field splitting parameter and the free ion separation 3F 3P, given by P. Since the complexes deviate from the point charge electrostatic model and orbital interaction between the metal and ligands occurs, the experimental energies of the various states then differ from the theoretical energies. To take this account, we can use equation 2 to calculate a value of the 3F 3 P(P) separation in the complex rather than use the free ion 3F -3 P separation. This we do by substituting an experimental value (for 3T1g(F) or 3T1g(P) in equation 2. viii) Obtain the Racah parameter B, for each ligand. The . Pcomplex nephelauxetic ratio = ---------Pfree ion Use the value given above for Pfree ion. ix) Arrange ligands in order of decreasing value. This gives the nephelauxetic series. x) The energy versus correlations for 3T1g (P) and 3T1g(F) deviate from linearity, why? References: Cotton & Wilkinson Lewis & Wilkins Cotton Sutton Manch & Fernelius Forster & Goodgame Drago Advanced Inorganic Chemistry Modern Coordination Chemistry J. Chem. Educ.1964, 41, 466. J. Chem. Educ. 1960, 37, 498. J. Chem. Educ. 1961, 38, 192 Inorg. Chem. 1965, 4, 823. Physical methods in Inorganic Chemistry.

APPENDIX 5A

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Inorganic Chemistry Year 3

Preparation of Nickel(II) Complexes: 1) Ni(bipy)3SO4 Warm an aqueous solution containing 15 g of bipyridyl and 6 g of NiCI2.6H2O. Cool and filter. Dissolve 5 g of the chloride and add 5 cm3 of a 1M solution of Na2SO4. Ni(bipy)3SO4 crystallises out. Reference: J. Chem. Soc., 1971 (A), 1637, 1640 2) Ni(en)3Cl2.2H2O: 2.8 g of 70% aqueous ethylenediamine is added to a solution of 2.38 g (0.01 mol) NiCl2.6H2O in 100 cm3 of water . The purple solution is filtered to remove the small amount of anhydrous iron oxide which precipitates and is then evaporated to a volume of 60 to 70 ml on a steam bath. Two drops of ethyelediamine are added, and the solution is cooled in an ice bath. The orchid-coloured crystals that from are collected by suction, washed twice with 95% ethanol, and air-dried. The yield is 2.86 g (80%). Several more grams may be recovered from the mother liquor by adding ethanol and cooling. 3) Ni(NH3)6CI2: Dissolve 2 g NiCl2.6H2O in 3 cm3 water. Add 6 cm3 NH3 and heat for 10 min. but do not boil. (Use fume-hood.) Then cool the solution in an ice bath and slowly add 6 cm3 ethanol with stirring. Filter with suction. Wash the precipitate with a little cold conc. NH3, followed by alcohol and acetone. Suck the solids dry. Record your yield. 4) Ni(DMSO))6Cl2: Dissolve 2 g of NiCl2.6H2O in 20 - 50 cm3 of ethanol and mix with the same volume of ether, follow by 3.9 g of dimethylsulfoxide (DMSO). Cool the mixture in the refrigerator until crystals are formed. Filter and dry in desiccator. Reference: J. Inorg. Nucl. Chem., (1961), 16, 219. 5) K4Ni(CNS)6.4H2O: Dissolve 0.01 mole of Ni(SO4).7H2O and KSCN in water (Work out appropriate amounts). Evaporate to dryness. Extract with absolute alcohol. Filter off the K2SO4 and concentrate the alcoholic solution to obtain the complex. Reference: Inorg. Chem. 4 (1965), 715, 823.

EXPERIMENT 6: THE EFFECT OF SYMMETRY ON THE INFRARED

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Inorganic Chemistry Year 3

SPECTRUM OF THE SULPHATE GROUP. INTRODUCTION Any regular tetrahedral AB4 molecule or ion should exhibit only two fundamental absorption in the infrared spectrum. The vibrational modes which give rise to these absorption may be described roughly as stretching and bending modes; both are triply degenerate. In the case of an ionic sulphate two strong infrared absorption are in fact observed. If, in a given crystal, the symmetry of the environment of the sulphate group is less than tetrahedral, then additional weak absorption may be seen due to vibrations which are forbidden when the fill tetrahedral symmetry is applicable. Complexes are known in which the sulphate group is ionic, monodentate or bidentate, and the splitting and changes of intensity of absorption bands due to that group beautifully illustrate the effect of progressively lowering the symmetry of the ion. EXPERIMENTAL Record the IR spectra of the following as Nujol mulls (SEE DEMONSTRATOR): i) ii) iii) iv) a simple ionic sulphate [Co(NH3)6] 2(SO4)3.5H2O [Co(SO4)(NH3)5]Br [Co(en)2(SO4)]Br

The second band of the sulphate ion (due to bending of the O-S-O angles) will not appear in the region covered by our spectrophotometer. Preparation of Complexes (ii) Hexamminecobalt (III) sulphate pentahydrate. First prepare hexamminecobalt(III) chloride as follows. Dissolve 12 g of ammonium chloride and 18 g of cobaltous choride, CoCl2.6H2O, in 25 cm3 boiling water. Add 1 g of decolourising charcoal and cool in ice. Add 40 cm3 concentrated ammonia and the solution at 10C or lower . Add slowly, in small portions, 35 cm3 of 20 volume hydrogen peroxide, briskly shaking the solution during the addition. Gradually raise the temperature to 50-60C and keep the flask at this temperature, with frequent shaking, until the last trace of pink coloration is removed. Cool and filter. Transfer the crystals to a beaker containing a boiling solution of 5 cm3 concentrated hydrochloric acid in 150 cm3 water. When all the solid, except the charcoal, has dissolved, filter the liquid while still hot. Add 20 cm3 of concentrated hydrochloric acid to the filtrate and cool the solution in ice. Collect the golden brown crystals and dry them by washing with acetone. If necessary the complex may be recrystallized from water containing a trace of hydrochloric acid.

29

Inorganic Chemistry Year 3

Dissolve 5 g of [Co(NH3)6]Cl3 in 50 cm3 hot water and mix with 50 cm of 20% sulphuric acid. Heat the solution to 60C and add 25 cm3 of 95% alcohol. Warm for a few minutes on a water bath to dissolve the solid and set aside to crystallize. After 24 hr., crystallization should be complete; wash the crystals at the pump with 95% alcohol until the filtrate is neutral. Dissolve the salt in hot water and precipitate by addition of alcohol. Filter and wash with alcohol until acid-free. Dry in air. If required, further recrystallisation may be effected from hot water.
3

(iii) Sulphatopentamminecobalt (III)bromide. First prepare chloropentamminecobalt(III) chloride as follows: (Note, this compound is one of the most important of the cobaltammines and is the starting substance for the preparation of many coordination complexes of cobalt). Co2+ + NH4+ +4NH3 + H2O2 [Co(NH3)5H2O]3+ [Co(NH3)5H2O]3+ + 3Cl [Co(NH3)5cCl]Cl2 + H2O

Dissolve 8 g of ammonium chloride in 48 cm3 of concentrated aqueous ammonia in a 500 ml Erlenmeyer flask. While continuously agitating the solution with a magnetic stirrer, add 20 g of finely powdered cobalt(II) chloride hexahydrate in small portions. With continued stirring of the resulting brown slurry, slowly add 13 cm3 of 30 per cent hydrogen peroxide from a dropping funnel. When the effervescence has ceased, slowly add 48 cm3 of concentrated HCl. Continue the stirring on a hot plate, holding the temperature at about 85C for 20 min; then cool the mixture to room temperature and filter off the precipitated [Co(NH3)5Cl]Cl2. Wash with 30 cm3 of ice water in several portions, followed by 30 cm3 of cold 6M HCl. Dry the product in an oven at 100C for several hours. The yield is about 15 g. Stir 8 g of [CoCl(NH3)5]Cl2 with 29 g of concentrated sulphuric acid in a porcelain dish: add the acid in small portions so that the evolution of hydrogen chloride gas is not too violent. When evolution has ceased, heat the resulting oily mass on a boiling water bath for 4 hr., during which more hydrogen chloride will be given off. Dilute with water and continue heating on the water bath until there is no more evaporation. Pour the liquid into a beaker and dilute with two volumes of water. If it is necessary to filter, do this as quickly as possible. Leave it for 24 hours, whereupon the acid sulphate precipitates in good yield, as shining, rectangular violet-red plates. Decant the strongly coloured mother liquor and transfer the crystals to a sintered-glass filter. Wash with 95% alcohol and dry in the air. Dissolve 4 g of the acid sulphate in 120 cm3 cold water and treat the solution with a mixture of 20 cm3 concentrated hydrobromic acid (b.p. 125) and 80 cm3 water. Gradually add alcohol, whilst stirring, to precipitate the product as a fine violet-red crystalline powder. Wash with alcohol until acidfree and dry in air.

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Inorganic Chemistry Year 3

iv) Sulphatobis(ethylenediamine)cobalt(III) bromide. First prepare trans-dichlorobis(ethylenediamine)cobalt(III) chloride as described in Experiment 1. Add 10 g of trans-[Co(en)2CI2]Cl to 20 cm3 of concentrated sulphuric acid in a beaker. When the initial effervescence has subsided, heat gently. The complex slowly dissolves with evolution of hydrogen chloride and a violet solution results. Raise the temperature to 120C until the evolution of gas ceases and then allow the oil to cool. Pour into 1 litre of alcohol which is continually stirred to prevent formation of an oil. Filter off the solid, wash with alcohol and then with ether. Dry in vacuo. Dissolve the deliquescent solid in a minimum volume of water and treat with a saturated aqueous solution of 5 g. lithium bromide then leave in a refrigerator at 0C for 3 days. Filter off the purple crystals, wash with alcohol and then ether. Air dry the product. If the mother liquors are left for a further three days a second crop of [Co(en)2(H2O)(SO4)] Br.H2O will be obtained. Heat the powdered product at 110 for 24 hr. in an oven. Recrystallise the [Co(en)2(SO4)] Br by dissolution in a minimum volume of cold water and addition of sodium bromide. The product crystallizes as short purple needles. QUESTIONS 1. List the symmetry of the sulphate groups in each of the complexes. 2. Identify the bands due to the sulphate group in the IR spectra of the complexes. 3. Draw out the rough form of the vibration giving rise to each absorption REFERENCES. K. Nakamoto et al. J.A.C.S. 79, 4904 (1957). C.G. Barraclough and M.L. Tobe J.C.S. 1993 (1961).

31