Experiment 6. Alfred Werner, Early Insights on the Composition and Structure of Transition Metal Coordination Complexes.

Coordination compounds of the transition metals were viewed as a mystery by nineteenth century chemists because they appeared to defy the usual rules of valence. Hence, the label complex compounds. The modern study of coordination chemistry is viewed to have begun with the work of Alfred Werner at the turn of the century, culminating with the Nobel Prize in chemistry in 1913. By Werners time it was known that a series of compounds could be formed by treating cobalt(III) chloride with ammonia. Note that the last two members of the Complex CoCl3 6 NH3 CoCl3 5 NH3 CoCl3 4 NH3 CoCl3 4 NH3 Color Yellow Purple Green Violet Early name Luteo complex Purpureo complex Praseo complex Violeo complex

list have the same formula but very different properties. Further, it was known that by treating each of the compounds in the table with Ag(NO3) solution different yields of AgCl could be obtained. CoCl3 6 NH3 was found to form three equivalents of AgCl, CoCl3 5 NH3 two equivalents, and for both forms of CoCl3 4 NH3 one equivalent. This led Werner to conclude that the last two classes of compounds contained two types of chloride, chloride present as a counter ion and chloride covalently bound to the Co atom. The formulas could be revised to reflect this difference as [Co(NH3)6]Cl3, [Co(NH3)5Cl]Cl2, and [Co(NH3)4Cl2]Cl, where chlorides appearing outside the brackets serve as counter anions for the charged complex ions. This early hypothesis received confirmation when CoCl3 3 NH3 was found to be a neutral molecule, [Co(NH3)3Cl3]. Next, Werner addressed the question of structure with an approach used by organic chemists in elucidating the structures of substituted aromatic compounds, namely isomer counting. Structures considered included a planar hexagon (benzene-like) with the Co at the center, a trigonal prismatic

Formula MA5B MA4B2 MA3B3

Planar 1 3 3

Trigonal Prism 1 3 3

Trigonal Antiprism (Oh) 1 2 2

Expt 1 2 2

arrangement of eclipsed triangular faces, and a trigonal antiprismatic structure with staggered triangular faces as an octahedron. The number of possible isomers for each structure could then be compared to the number observed experimentally. It was clear from this exercise that the geometry about the Co was octahedral, and this could further account for the Violeo (cis) and Praseo (trans) isomers of CoCl3 4 NH3 as [Co(NH3)4Cl2]Cl. Introduction of the chelating ethylenediamine ligand (H2NCH2CH2NH2, en) in place of the ammine ligand (:NH3) added a new consideration to the stereochemistry of the octahedral complexes. The [Co(en)3]3+ cation has D3 symmetry, rather than the Oh symmetry of [Co(NH3)6]3+. The absence of a mirror plane in the point group symmetry of [Co(en)3]3+ results in the presence of rightand left-handed optical isomers. The left-handed isomer, visualized by the rap of ligands from the lower triangular face of the octahedron to the upper face, is

N N Co N N N N N N

N N Co N N
3+

called the isomer, ([-Co(en)3] ), and the right-handed isomer is [-Co(en)3]3+. Optical activity can be observed by measuring light rotation using a polarimeter on a resolved sample. Similarly [cis-Co(en)2Cl2]+ with C2 symmetry can be resolved into and isomers, while [trans-Co(en)2Cl2]+ with D2h symmetry has only one isomeric structure. This was further confirmation to Werner of the octahedral structure of 6-coordinate complexes. The use of d6 Co(III) in these studies was key. As a low-spin t2g6 metal ion it is kinetically stable, permitting isolation of structural isomers without equilibration due to ligand dissociation. Further, the rotation barrier that might equilibrate optical isomers is high for a t2g6 metal ion, making it possible to resolve optical isomers. In our experimental procedure we will first prepare [trans-Co(en)2Cl2]+ as the kinetic product of our synthetic procedure. This product is favored by the trans-directing influence of the strongly bound chloro ligand. Since, from bond-strength considerations, the Cl- ligands would prefer adjacent coordination sites trans to more weakly bound nitrogens, the thermodynamically stable cis isomer may be formed by heating the trans isomer in solution. [cis-Co(en)2Cl2]+ will form as a mixture of optical isomers; the isomers will be separated by crystallization with a chiral anion. The extreme kinetic stability of low-spin Co(III) requires that we begin our synthesis with labile high-spin Co(II). Aerobic oxidation of the Co(II) ion will form the kinetically stable complex of Co(III).

Part I. Synthesis of trans-Dichlorobis(ethylenediamine)cobalt(III) Chloride, [trans-CoCl2(en)2]Cl. Materials CoCl2 6 H2O, 10% ethylenediamine solution, conc. HCl. Equipment Glassware, magnetic stirrer, hot plate, Hirsch filter funnel. Dissolve 2.0 g CoCl2 6 H2O in 10 mL of water and add 6.0 mL of 10% ethylenediamine. Assemble the arrangement shown below to aerate the solution. Clamp the reaction tube in a hot water bath (90 - 95 C) and connect the side-arm to a water aspirator. Turn on the aspirator to draw air through the solution at a slow but steady rate. The purple reaction mixture is maintained under these conditions for the period of one hour, with periodic addition of water to maintain a constant volume. After one hour disconnect the apparatus, remove the tube from the bath, and allow it to cool to approximately 60 C. Using a Pasture pipet, slowly add 4 mL of concentrated HCl down the inlet tube. Reconnect the aspirator and place the tube back in the hot water bath. A Adjust the aspirator so that a steady stream of air is pulled through the solution. Continue heating until the volume of the solution is reduced to the point that crystals of the product are evident in the tube. Disconnect the apparatus and place the tube in an ice bath to cool. Scrape solid product in the tube free from the walls, and isolate by vacuum filtration. Wash the green crystalline solid with two 5 mL portions of cold methanol, which is added to the original filtrate to obtain more product. Once all the product is isolated wash it with two 5 mL portions of diethyl ether and allow to air dry. The green crystalline product isolated by this procedure is a hydrated form of [trans-Co(en)2Cl2]Cl 2 H2O. Characterization Record the IR spectrum (KBr pellet) and UV-vis spectrum for comparison with the cis isomer. Be sure to determine the concentration of the solution accurately to calculate values for molar extinction coefficient. Part II. Synthesis of cis-Dichlorobis(ethylenediamine)cobalt(III) Chloride, [cis-CoCl2(en)2]Cl. Once characterization on the trans isomer is complete, place the sample in a 10 mL beaker and dissolve it in 3.0 mL of water. Heat the green solution carefully on a hot plate to evaporate the water without violently boiling the solution. As the solution evaporates a deep violet sample of the cis isomer will form. Heat the mixture to dryness and isolate the sample of [cis-Co(en)2Cl2]Cl for characterization.

Characterization Record the IR spectrum (KBr pellet) and UV-vis spectrum for comparison with the trans isomer. As before, be sure to determine the concentration of the solution accurately to calculate values for molar extinction coefficient. Part III. Resolution of the and Isomers of [cis-CoCl2(en)2]Cl. Once characterization on [cis-Co(en)2Cl2]Cl is complete the remaining portion of the sample will be separated into right- and left-handed optical isomers. Earlier the distinction between and isomeric structures was made on the basis of structure. An experimental distinction can be made on the basis of the direction of light rotation by the optical isomer. In fact, the right-handed structural isomer () rotates polarized light in a left-handed sense, and the isomer rotates light to the right. With this, a second nomenclature system can be introduced based on this experimental observation where right light rotation is termed dextrorotary (d or +) and left rotation is levorotary (l or -). So, -cisCo(en)2Cl2+ is also D (+)-cis-Co(en)2Cl2+ and -cis-Co(en)2Cl2+ is L (-)-cisCo(en)2Cl2+. The polarimeter that is typically used to measure light rotation is shown below. In order for the rotated polarized light to pass through the analyzer prism,

this prism must be rotated, relative to the polarizing prism, to the right or left by an angle that is equal to the rotation caused by the sample. Thus, the direction and number of degrees of rotation may be measured experimentally. Specific light rotation at a particular wavelength is [] is defined as [] = /lc where is the rotation angle, c is solution concentration in grams of solute per mL of solution, and l is the light path length in decimeters. Units of molar rotation, [M] are more commonly used as [M] = M[]/100 where M is the molecular weight of the substance. The rotatory power of a substance varies with the energy of the incident light and the plot of [M] vs is called the optical rotatory dispersion (ORD) curve. The ORD curve for D (+)-cis-Co(en)2Cl2+ is shown below; the curve for L (-)-cisCo(en)2Cl2+ would be the mirror image with similar wavelength dependence but opposite in sign.

In the experimental procedure, the optical isomers of [cis-Co(en)2Cl2]+ will be separated by isolating one isomer using the antimony-D-tartrate anion, [Sb(O6C4H2)(H2O)]-. Materials - [cis-Co(en)2Cl2]Cl, potassium antimony-D-tartrate hydrate Procedure In a 50 mL Erlenmeyer flask containing a magnetic stirring bar, dissolve 0.84 g (2.5 mmol) of potassium antimony-D-tartrate hydrate in 10 mL of water. Warm the mixture on a hot plate (without boiling!) to dissolve the solid. In a 50 mL beaker, dissolve 0.73 g (2.5 mmol) [cis-Co(en)2Cl2]Cl in 20 mL of water. Transfer the solution in the beaker to the flask. Heat the solution to 70 - 80 C with stirring for 45 min. A pale violet precipitate will form over this time period. Cool the flask to room temperature, and isolate the solid by suction filtration. Wash the solid with 5 mL of ethanol and then with 5 mL of diethyl ether. Evaporate the filtrate to obtain the second optical isomer. Characterization Prepare a saturated solution of the solid in very hot water. Determine the specific rotation of the product using a polarimeter. Specific rotation must be measured quickly as the product will precipitate from solution upon cooling. Questions 1. Use the isomer counting approach to analyze the structure of Pt(NH3)2Cl2. Two isomers can be obtained for the complex; is it tetrahedral or square planar? Could a similar argument be used to assign the structure of Pt(en)Cl2?

2. The use of complexes prepared with the Co(III) ion in this experimental procedure take advantage of two important properties, kinetic stability and a slow rate of isomerism. Describe how the low-spin d6 configuration is responsible for these properties. Could similar experiments be carried out using complexes of high-spin Fe(III)? 3. What is the Trans Effect? Describe how the Trans Effect leads initially to the trans isomer as the kinetic product and, ultimately, to the cis isomer as the thermodynamic product.