Experiment 1

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Inorganic Chemistry II

LABILE COMPLEXES
References
1. 2. 3. Chang, "Chemistry", 5th Edition, Chapter 23, and section 17.5. Shriver, Atkins, and Langford, "Inorganic Chemistry", Chapter 15 Student Folder The Chemistry of Manganese
2+

Background
Metal complexes are often formed when anions or neutral molecules (i.e. ligands) become attached to a central metal atom. The bond is usually the result of the donation of an electron pair from the ligand to the metal ion. Even "simple" metal salts such as NiCl2.6H2O, actually contain a metal hexaaquo complex with six water molecules coordinated around the central Ni2+ ion, shown at right. H 2O H 2O H 2O Ni OH2
[Ni(H2O)6] 2+ or Ni (aq)
2+

OH2 OH2

Aquo metal complexes are often used as the starting material in the preparation of complexes with different ligands. This is because many aquo metal complexes are labile, that is the water molecule ligands exchange rapidly with other ligands. Thus, so long as an excess of the desired ligand (e.g. NH3) is present, it is possible to form a new complex (e.g. [Ni(NH3)6]2+) fairly quickly. Because the complexes you will investigate in this experiment are labile, you will find it possible to interpret many reactions as a competition between water molecules and other potential ligands to coordinate to the metal ion. Often the most difficult step in the preparation of a solid coordination compound is to determine the best way to isolate the complex from any by-products. This will depend, in part, on the type of complex formed (i.e. ionic or neutral, anionic or cationic). In part A an anionic metal complex is prepared which is separated by fractional crystallisation from the reaction mixture. A more soluble ionic salt is formed as a by-product, so the main product is purified by recrystallising from water (neutral complexes often have low solubility in water). In Part B, another anionic metal complex is prepared. As there are no by-products, the complex can be isolated as a salt and precipitated with a suitable solvent or at a suitable temperature. In Part C, a neutral metal complex is prepared by adding a negative ligand, L-, to the positive metal ion in solution. In this case you will need to initially oxidize the metal ion to reach the desired oxidation state. The ligand is added to the aquo metal complex in the form HL and to maximize the yield (i.e. to push the equilibrium in favour of the products) the H+ by-product is removed by adding base to the solution: Mn+(aq) + m HL [MLm](n-m)+ + m H+ + xH2O
OHH2O

Experiment 1

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Inorganic Chemistry II

When carrying out the qualitative tests on these labile complexes remember that small concentrations of the aquated metal ion, Mn+(aq), and free ligand, L, will exist in solution as the equilibrium shown below is rapidly established. [MLm]n+ + x H2O Mn+(aq) + mL

Mn+(aq) may be removed from the equilibrium by: addition of OH-, to form an insoluble hydroxide, or a hydroxo complex; by addition of S2- to form an insoluble metal sulfide; or by addition of a better ligand to form a new complex. Addition of H+ may remove L from the equilibrium in the form of LH+ (e.g. many complexes containing ammonia ligands are decomposed in acid solution as NH3 is turned into NH4+) leaving Mn+(aq) in solution; alternatively the addition of another metal ion may cause the formation of a new metal complex leaving the first metal as a Mn+(aq) species. These events may lead to complete dissociation of the original complex, shown below:
[MLm]2+ + H2O M2+(aq) + L

OH- or S2- or another ligand, L'

M(OH)2 or MS or [ML'n]

H + or another metal ion

LH+ or new metal complex

Aim of the Experiment

To prepare and isolate three different metal complexes and then to examine their properties.

Outline: (experiment undertaken as a group of 3 people)

1. 2. 3. Preliminary Questions - to be done before you enter the laboratory. In Part A you will prepare the complex K3[Fe(C2O4)3].3H2O and then test its reaction with acid and photodecomposition. In Part B you will prepare the complex [NEt4]2[CoBr4]. In the tests, you will add, to solutions of complex, various ligands which will compete with Br- for coordination positions on the Co2+ ion. In Part C you will prepare [Mn(acac)3] and examine its stability when added to water.

4.

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Inorganic Chemistry II

Preliminary Questions
All the information you need to answer these questions can be found in the background notes to this practical or the student folder which is located on the benches in the laboratory. If you feel in need of a revision of the basic concepts involved in metal complexes refer to your first year text or Inorganic Chemistry 2nd Edition by Shriver, Atkins and Langford. 1. After reading the experimental section formulate an equation for the preparation of each complex. (Several equations are required in Part C). Give relevant equations omitting the spectator ions. Eg. 2. 3. 4. Part A: Fe3+ + 3C2O42- [Fe(C2O4)3]3-

For each complex sketch the stereochemical configuration. Note instances where isomers are possible. What is a labile complex? Why is the separation and isolation of isomers not feasible for a labile complex? Which molecule is more polar: water or ethanol? By considering the way water and ethanol interact with the cobalt ion, Co+, suggest why ethanol is used as a solvent instead of water in the preparation of [CoBr4]2-.

Experimental
All tests are carried out using test tubes. If a test doesn't appear to give any result, repeat it and/or consult a demonstrator. Give concise interpretations of your observations, identifying colour changes with new species formed. Many of the results can be understood on the basis of competitive equilibria. Give equations wherever possible. Remember that most basic and inorganic anions may function as ligands (some anions such as ClO4 , - compounds NO3 , and BF4 are notable exceptions and usually do not coordinate to metal ions in aqueous solutions). Throughout this experiment, both in the preparations and tests, you should be aware of the lability of the complexes and observe that the reactions are generally rapid. (Occasionally the observed reaction rate may be governed by the rate of dissolution of a reagent). A. Potassium tris(oxalato)ferrate(III), K3[Fe(C2O4)3].3H2O To understand some of the reactions it is useful to know that the colour of the Fe3+(aq) is pale -violet- to colourless in dilute solution but yellow in the presence of coordinating anions, e.g. Cl , OH , and SO42-.
O Prepare aqueous solutions of potassium oxalate, K2(C2O4).H2O, O (FW 184.24) (12.0 g in 20 mL) and Fe(NO3)3.9H2O (FW 404) (8.1 g in 10 mL). With stirring add the metal ion solution slowly to the hot potassium OH oxalate solution. Allow to stand for a few minutes then cool the mixture in HO oxalic acid an ice-bath and filter off the product. Dissolve the crude product in hot water (about 15 mL), filter hot, and cool in an ice-bath. Collect the crystals and wash with ethanol, followed by acetone and then air-dry by suction. Record the yield and percentage yield of the complex.

What impurities are removed by recrystallising the complex from water?

Experiment 1 Tests 1.

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Inorganic Chemistry II

Test separately the effect of (i) 1M hydrochloric acid, and (ii) 1M nitric acid on ferric nitrate by adding a small quantity of crystals to about 1 mL of each acid in separate semimicro test tubes and shake gently. Test both resulting solutions by adding a few drops of ammonium thiocyanate solution. Treat a sample of your complex in the same way with both acids. Observe the colour produced by adding the o-phenanthroline reagent (located on your bench) to a small volume of (i) dilute ferrous sulfate solution, and (ii) dilute ferric nitrate solution. Both Fe2+(aq) and Fe3+(aq) are strongly complexed by o-phenanthroline forming a complex ion. [ML3]n+

2.

o-phenanthroline

3.

Prepare a dilute solution of your complex in water and divide into two. Add equal amounts of the phenanthroline solution to both aliquots and store one in the cupboard (i.e. in the dark) and place the other near a window. Compare the colours of the two solutions after some time. Suggest a possible explanation for these observations, giving equations wherever relevant. (Clue: Fe(3+) complexes are oxidising and oxalate ions are reducing.)

B.

Tetraethylammonium tetrabromocobaltate(II), [NEt4]2[CoBr4]

To understand some of the reactions it is useful to know that the colour of both Co2+(aq) and Co(OH)2 is pink. Prepare solutions of CoBr2.6H2O (FW 326.8) in ethanol (1.63 g in 5 mL) and tetraethylammonium bromide NEt4Br (FW 210.2) in ethanol (2.10 g in 5 mL). Warm these solutions on a steam bath until the salts have dissolved, then mix these solutions. Heat the solution for a few minutes. Cool the solution for a few minutes in an ice-bath. Filter off the product in a dry quickfit Buchner filter (keep free of water!). Press the solid down in the filter with a spatula, then wash with a little ethanol, then acetone. Dry first by suction then briefly in the oven at 80-100C until free of acetone. Record the yield and percentage yield. Why does red-violet CoBr2 give a blue colour when dissolved in ethanol? Tests Use a solution (about 1 mL from a Pasteur pipette) of the complex in water in a test tube for tests 1 and 2. 1. 2. Add sufficient solid LiCl to saturate the solution. Add a little solid NH4SCN Check that the precipitate obtained dissolves in 1 M H2SO4, and give an explanation by considering the equilibria that exist in solution.

For tests 3 and 4 use a solution of the complex in ethanol in a test tube by warming some complex in ethanol in a small beaker on the steam bath. Decant a little for each test. 3. Add a few crystals of AgNO3, shake and leave stand. When the precipitate settles, observe the colour of the solution. What is the precipitate, and what species is responsible for the colour of the solution?

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Inorganic Chemistry II

Add a small amount of solid HgBr2. What is the electronic configuration of Hg in the solution. Why is the blue colour discharged? Suggest a formula for the precipitate obtained in terms of a Hg(II) complex. Tris(acetylacetonato)manganese(III), [Mn(acac)3]

C.

In this case the manganese atom, in the starting metal salt MnCl2.4H2O, is in the 2+ oxidation state, whereas the metal complex you are to make has manganese in oxidation state 3+. Thus an oxidizing agent, KMnO4, is added to the solution during the preparation so that the oxidation state of 3+ is achieved and [Mn(acac)3] formed. To help you identify various complexes remember that Mn2+(aq) and Mn(OH)2 are very pale pink to colorless, Mn3+(aq) is red violet, and Mn(OH)3 is dark brown.
CH3 Dissolve MnCl2.4H2O (3.0 g) and Na(CH3COO).3H2O (8.0 g) H3C in water (120 mL), and to the stirred solution slowly add acetylacetone (12 mL). Treat the resulting two-phase system with 2% aqueous O O KMnO4 solution (30 mL). After stirring for 5 minutes add, in small acetylacetone amounts with stirring, sodium acetate solution (8.0 g in 30 mL of "Hacac" water). Heat the mixture to 60-80C (hotplate) and then leave on the steambath for 15 minutes. Cool in ice-water to room temperature or below - this is important for speedy filtration. Then collect the product on a Quickfit sintered glass funnel. Wash the product with ice cold water, then apply suction for a further 5 minutes. Transfer the product to a watchglass and dry in the oven at 80C for 30 minutes. Record your yield and percentage yield.

Why is sodium acetate used in this preparation? (Consider the equilibria that exist and the desired product). Why is permanganate used as the oxidant? Tests Compounds of manganese in the 3+ oxidation state are unstable and tend to disproportionate. The tests described below are designed to investigate this aspect of the chemistry of the complex. The complex has been simmered in water, and the suspension centrifuged, washed with acetone then dried. This material is in a bottle labeled SECTION C - test material. Use this material in tests 1, 2 and 3. 1. Test the reaction of the solid by heating with a few drops of concentrated hydrochloric acid. Test the resulting solution with dilute sodium hydroxide and gentle heating. Record your observations. Repeat the tests in 1 above using a small amount of MnO2 instead of the complex. Make a dilute solution of manganese chloride and examine the effect of adding dilute sodium hydroxide and warming gently.

2. 3.

From the results of the above tests, and by consulting the notes on the "Chemistry of Manganese" which are provided in the folder, account for your observations, giving chemical equations wherever relevant.

Report
For the preparations, give equations for all the reactions involved, the yields and percentage yields, and answers to listed questions. For the tests, give the results (colours, etc.) with interpretations and equations.