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Experiment 2 Geometrical Isomers: Cis & Trans Isomers of Dichlorobis(ethylenediamine)cobalt(III) Chloride


Prelab assignment Calculate the mass of [Co(en)2Cl2]Cl2H2O needed to make 5 mL of a 0.0150 M aqueous solution of this complex (en = ethylenediammine, shown in Figure 1 below). You must have precisely this molarity of solution to perform this experiment, so calculate carefully and accurately. In the Data Analysis section of your lab report, you will calculate the molar extinction coefficient of absorbance peaks in spectra of these isomers, using Beer's law. You cannot accurately calculate any molar extinction coefficient if you do not know the precise molarity of your solution.

Introduction Geometrical isomers are metal complexes in which the coordinating ligands are present in the same proportion but vary in the arrangement of the ligands around the central metal atom. Despite always having identical chemical formulas, geometrical isomers often have widely different properties, such as magnetic moments, colors, bond strengths, and reactivities.
Cl Co N H2 Cl N H2 H2 N Cl Cl Co N H2 H N 2 NH2

H2 N

H2 N

trans-[CoCl2(en)2]+

cis-[CoCl2(en)2]+

Three Views of Octahedral Complexes

Figure 1. Geometrical isomers from octahedral coordination complexes. The cobalt complexes that we will investigate, trans- and cis-[Co(en)2Cl2]Cl (Figure 1), are both six coordinate. There are six ligands bound to the central metal atom in an octahedral structure. An octahedron is a geometrical solid with six vertices, each vertex being at 90 degrees

2 to its four nearest neighbors and 180 degrees from the remaining vertex. When viewed as a polyhedron, it can be seen that an octahedron has eight triangular faces. In a perfect octahedron the faces are all identical equilateral triangles. Because we have a mixed ligand set [chloride and ethylenediamine (en), where en is a bidentate ligand that has two metal binding sites], our molecules will have a distorted octahedral structure. Complexes of cobalt(III) undergo ligand substitution reactions relatively slowly and so tend to be stable to ligand exchange even when solvated with water molecules. This allows us to isolate metastable species by crystallizing them before they can convert to the most thermodynamically stable form. Despite the slow substitution chemistry of cobalt(III) complexes, the uncomplexed Co(III) ion itself is not stable in water due to the hydrolysis/reduction reaction shown below: 4 Co3+ (aq) + 2 H2O (aq) 4 Co2+ (aq) + 4 H+ (aq) + O2 (g) We can ensure a constant (if small) supply of Co3+ during our reaction by bubbling air through our reaction solution, thereby supplying O2 and keeping the above equilibrium lying to the left. We will also use the stronger oxidizing agent, hydrogen peroxide (H2O2), to oxidize cobalt to Co+3. Once Co3+ is coordinated by the en and Cl ligands, it is stable against reduction by water back to Co+2. Throughout these preparations, note any color changes in your laboratory notebook. These changes are indicators of changes in the coordination sphere around the cobalt ion.

3 Beer's Law The Beer-Lambert law is an empirical equation that relates the number of light-absorbing molecules in a sample, the magnitude of the light absorption, and the inherent ability of that molecule to absorb light.

The equation is A = L c, where:

A = the magnitude of an absorption of light L = the length of the sample through which the light beam travels, and c = the concentration of the absorbing molecules in moles/liter.
The length of the samples L on all UV-visible instruments is now standardized at 1 cm. The absorbance A is read off of the y-axis of the electronic spectrum for each absorbance peak, and the concentration c of the sample should be precisely calculated. One can therefore solve for

, the molar extinction coefficient of the particular absorption you are studying (units are
liters/mole-cm). The extinction coefficient is a measure of the inherent strength, or magnitude, of the electronic transition that gives rise to the absorption of light. Some electronic transitions are "forbidden" by selection rules of quantum mechanics or symmetry (we will study this further in Experiment 4). These transitions will have small extinction coefficients, perhaps on the order of 1.0, showing that the electronic transition is inherently not a favorable one, and the absorbance will be low. Some electronic transitions are very favored, not forbidden by any selection rules, and may have extinction coefficients of up to 1 x 103, which would give rise to a very strong absorbance even at a low concentration. The geometry of a complex influences the favorability and wavelengths of its electronic transitions considerably. In the Data Analysis section of your lab report, you will calculate the molar extinction coefficient of each absorbance peak in your spectra for the two geometric isomers, using Beer's Law. In the Discussion section you will comment on the similarities or differences of the spectra and coefficients, and relate them to the geometry of each complex.

4 Experimental Procedure

SAFETY NOTES: Ethylenediamine may give off irritating vapors.


HCl and 30% H2O2 are extremely corrosive; H2O2 can react violently with organic solvents and substances, such as clothes, hair, paper, and dust. Wipe up all spills immediately with water. If skin or eyes are exposed, instantly flush the affected area with copious amounts of water for fifteen minutes. How to Filter Efficiently In this experiment, you will filter your reaction mixture in the preparation of the trans isomer in order to separate the solid crystals from the solvent. The procedures given here will make the filtering of any reaction mixtures in this and in all future experiments more efficient. The small white ceramic filter is called a Hirsch funnel, and the large white ceramic one is a Buchner funnel. Use the filter papers that are specifically cut and sized for each funnel. Attach a piece of rubber tubing to the sidearm of your filter flask, and attach the other end of this tubing to the sidearm of a vacuum source. Place your black rubber ring on top of the filter flask. Place your Buchner or Hirsch funnel on top of the black rubber ring or cone, and place an appropriately-sized piece of filter paper into the funnel. Wet the filter paper thoroughly with solvent: this makes the paper stick better to the funnel, and prevents solids from passing through the filter. Turn on the vacuum source and pour your solution and crystals into the funnel and onto the wet filter paper. To obtain a good seal between the funnel and the flask (and therefore a stronger vacuum and better filtration and drying of your crystals), press down hard on the top of the funnel to seal it firmly to the black rubber ring or cone. However, DO NOT break the filter or the flask, or cut your hand. When the solvent has passed through the filter, you may now add any other solvents that you are instructed to rinse, or wash, the solid crystals with. Again, as whenever you want solvent to pass efficiently through the filter, press down hard on the top of the funnel to seal it firmly to the black rubber ring or cone. Dry your crystals on the filter paper using the vacuum source by leaving the vacuum on and pressing down hard on the top of the funnel, to pull air through the solid and dry it.

Preparation of trans-[Co(en)2Cl2]Cl2H2O Start by making an air inlet for your sidearm test tube (see Figure 2, page 6 of this EP). This air inlet consists of a LONG (not short) Pasteur pipette inserted through a rubber stopper. Take care not to break the pipette when inserting it into the rubber stopper: do not push it, but twist it gently and very slowly. This will take some time. Apply glycerol to the inside walls of the rubber stopper to help the pipette twist in, but don't let your hands slide. Note that the pipette does not have to be fully inserted into the rubber stopper. It only has to be inserted far enough for the long tip to be immersed in the top of the solution in the test tube. The pipette tip does not have to be deeply submerged in the reaction solution, but should reach down below the surface about one inch. To assess whether pipette has been inserted far enough, fill the sidearm test tube with 9.5 mL of deionized water, and cap the tube with the rubber stopper/pipette. If the pipette tip extends about an inch below the water level, you have inserted the pipette far enough. Do not connect the sidearm of the test tube to the vacuum source at this time. Now take the rubber stopper/pipette off of the sidearm test tube, and dissolve 1.2 g of cobalt(II) chloride hexahydrate in 9.5 mL of deionized water in the tube. Add the small magnetic stirbar to the tube and stir the solution during the following additions. First add 2.5 ml of a 16% ethylenediamine solution to the test tube. Then slowly add 1.2 ml of 30% H2O2 solution dropwise this should take about 3 minutes. Finally, add 2.4 ml of concentrated HCl dropwise to the reaction mixture. Addition of peroxide and HCl will cause bubbling and heating of the solution; prevent the solution from splashing by adding the reagents slowly and stirring efficiently. Cap the sidearm test tube with the rubber stopper/pipette and attach the sidearm of the test tube to a vacuum source. Turn the vacuum on to pull air through the pipette and the test tube. Heat the test tube over a steam bath to remove water. The air being pulled through the test tube will help to speed the evaporation of the water solvent. Allow the solution to evaporate

Side Arm Test Tube Apparatus

7 until the volume is reduced to roughly 2 ml or less: green crystals (and possibly teal and/or dark blue ones) will precipitate. Cool the solution in an ice bath to precipitate as much complex as possible. If you do not see any precipitation at all, even after removing most of the solvent, try to make a tiny scratch in the bottom or side of the tube by gently scraping with a metal spatula, and cool the solution again. (DO NOT push the spatula through the bottom of the tube!) Filter to recover the crystals. The deep green product is trans-[Co(en) 2Cl2]ClHCl2H2O. Wash the crystals twice with 8 ml portions of methanol, and then with two 8 ml portions of diethyl ether. The methanol usually removes the HCl co-solvate, and the ether helps to remove excess water solvent and so dry the crystals. Dry the crystals as much as possible on the filter using the vacuum, and then collect them and spread them on a piece of filter paper to air dry. Try to physically separate the green crystals from any teal or blue products--these may be Co+2 complexes that were not oxidized by the peroxide, or Co+3 complexes that were not coordinated by the right ligands. Assume for this lab that your green washed crystals are trans[Co(en)2Cl2]Cl2H2O. Determine the yield of the green product only.

Preparation of cis-[Co(en) 2Cl2]Cl 2H2O Make 5 ml of a 0.0150 M aqueous solution of the trans isomer (the green crystals that you synthesized above) in a small Erlenmeyer flask. Heat this green solution over a steam bath for several minutes it should turn pale violet. If solvent is removed in an attempt to isolate the violet cis isomer, as we did when crystallizing the trans isomer, the loss of water causes some of the cis isomer to re-convert to the green trans product, producing a mixture of isomers. So, do not try to evaporate the water and isolate the cis isomer as a solid. Use the violet solution to acquire an electronic spectrum (see below).

Analysis of the Cobalt Complexes Acquire an electronic absorbance spectrum of both complexes in the visible and near-UV region (300 nm - 900 nm). Use about 5 mL of a 0.0150 M aqueous solution of each complex as your samples. Instructions for operating the UV-visible instruments are given on page 9 of this

8 EP, and are posted on the website. Label your spectra as the cis or trans isomer immediately after the acquisition, to avoid confusing the two.

How to Make UV Samples The plastic UV sample holders are called cuvettes; they hold solutions for which UV spectra will be acquired. Cuvettes have a full line marked at the top, but your sample solution does not have to fill the cuvette all the way up to the line. The UV beam passes through the center of the cuvette's length, and so if you are ever short of sample solution, you need not fill the cuvette all the way up, but just up to past the center. Cuvettes have two opposite sides frosted (for your fingers to hold), and the other opposite sides clear (for the beam to travel through). An arrow is marked on one clear side; this is the side that should be turned towards the beam when you place the cuvette in the instrument. In Experiment 2, the exact concentration of the UV sample solutions must be known, so follow the EP instructions to make those samples. However, in many experiments, knowing the concentrations of the sample solutions isn't necessary. You then can determine the "right" concentration by the color of the solution. The solutions should be colored (to give the most intense absorptions) but transparent (to not exceed the limit of the detector). One way to make such samples is to put a small quantity of solid sample, or a concentrated solution in which sample is dissolved, into the cuvette. Then add more of the pure solvent in which the UV spectrum is being taken. (For solid samples, draw the solvent and solid up into the pipette few times, to make sure the solid dissolves.) Then, if the color of the sample is too pale, more solid crystals or more drops of the concentrated solution can be added. If this doesn't make the sample dark enough, some can be removed from the cuvette and more solid or concentrated solution can be added, then more pure solvent. Repeat until the color is visible and transparent, but not deep and dark. If the sample is too dark, remove solution from the cuvette and fill it with pure solvent. Mix by drawing the sample up into the pipette a few times. If the sample is still too dark, remove some from the cuvette and dilute again with pure solvent. Repeat until the color is visible and transparent, but not deep and dark. Rinse out used cuvettes and throw them into the Trash, not the Solid Waste container.

How To Acquire UV Spectra

1. Place your sample and (if you are making your own blanks) a sample of pure solvent (the blank) into two separate plastic cuvettes. 2. Place the sample in the front holder. The TAs will usually have already put the appropriate blank in the back holder. 3. Click Start button at the bottom of the computer screen--it will acquire the spectrum. Click OK when done. 4. Select Peak Pick from the Operations menu. (Note that Peak Pick sometimes does not find one or more of your absorbances! Ask a TA how to fix this.) 5. Right-click in the absorbances table to not show the valleys, and to not mark the valleys. 6. Select Print Preview from the File menu--this shows your spectrum, absorbances, and wavelengths of peaks. 7. Go to File Menu, select Print. Select the number of copies you want printed. It prints the spectrum. 8. Close Print window. 9. Close the data file by clicking on OK. 10. Go to Properties under the File menu. Click on Delete. You may now get a screen that asks you whether you want to continue with the delete, although the file has not been saved. Be sure to click Yes. You must delete the old spectrum before a new one can be acquired . 11. Close File Properties window. The instrument is now ready to start with a new sample. Take your cuvette back to your bench and wash it out thoroughly. Then dispose of it in the Trash (not in the Solid Waste container).

10 Data Analysis 1. (7 points) Write the balanced redox reaction, including the half-reactions, between cobalt (II) and H2O2 that occurred during the preparation of the trans complex. H2O2 has oxygen in the -1 oxidation state. It is an oxidizing agent, and therefore is reduced during the reaction, giving H2O, in which oxygen is in the -2 oxidation state. The solution contains protons, from your addition of HCl. 2. (2 points) List in tabular form the wavelengths and absorbance values of all absorbances seen in your electronic spectra of the trans and cis isomers. Also list in the table the for each absorbance. Show your calculation of for all absorbances. 3. (2 points) Express the difference between the absorption coefficients of one complex, and those of the analogous absorptions of the other, as percentages . Show your calculations. 4. (5 points) Show with a drawing whether the cis and trans isomers are enantiomers.

Discussion 1. (6 points) Discuss how each isomer was prepared, what was done differently in their preparation, and what chemical species was used to favor one isomer over the other.

2. (12 points) What color of light is absorbed by each complex? Which has the larger o? Discuss the reason for the difference in o that the complexes show. (Consider the effect of strong field vs. weak field ligands on the dz2 orbital only. ) 3. (12 points) From examining your data, discuss whether one isomer or the other has transitions that are more allowed, how you know this, and why this would occur. Conclusions: (4 points) What differences in physical properties have you observed in these two geometrical isomers, and what practical uses could they be put to?

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Questions 1. (5 points) How many geometric isomers exist for complexes of the general formula MA3B3? Draw and name each of them. 2. (5 points) Co(III) exhibits a strong tendency to coordinate with ligands containing nitrogen. Is this consistent with the hard-soft acid-base (HSAB) concepts that we studied in Experiment 1? Explain your answer. 3. (5 points) How many valence electrons are present in the Co(II) and Co(III) ions? Show how you arrived at your answer.

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