A Comparison of Geometric Isomerism in Transition Metal Complexes Abstract

Figure 1: cis- and trans-Dichlorobis(ethylenediamine)cobalt(III) chloride

Coordination compounds are largely governed by their electronic configurations, as well as molecular symmetry. Chirality is observed in coordination compounds as well as follows the criterion of the absence of an axis of improper rotation. Octahedral complexes, such as dichlorobis(ehtylenediamine)cobalt(III) chloride have cis and trans isomers. However, the presence of both isomers doesnt imply that they are both optically active, as only the cis isomer is which can been seen by the structure. Platinum can form complexes with zero oxidation states, as well as tetrahedral, octahedral, and square-planar geometries. These complexes are important intermediates for other compounds and display the utility of platinum coordination compounds. Coordination compounds give rise to geometric isomers due to the exact position of the ligands around the central atom. Some positions and isomers are favored due to stability, but with influence the ligands can be repositioned to form other isomers, which can change the properties of the complexes. INTRODUCTION Metal complexes that consist of a metal atom or ion surrounded by multiple ligands have common structural arrangements, including isomers. Ligands are molecules or ions that act as Lewis bases and donate electrons to bond with an accepting central metal atom acting as a Lewis acid. These complexes are referred to as coordination compounds, and typically exhibit bright colors as a result of their electronic configurations. The structure of coordination compounds result from their electronic configurations, as well as molecular symmetry. Some common geometrical arrangements of ligands found in coordination compounds are tetrahedral, squareplanar, trigonal-bipyrimidal, and octahedral. Tetrahedral and square-planar complexes have a coordination of four, meaning the central atom is bonded to four surrounding ligands, while octahedral complexes have a coordination of six. Geometric isomerism in coordination compounds arises from the arrangement of the ligands around the central atom. That is, complexes with the same molecular formula can have different structures with the same symmetry arising in isomers, such as cis and trans.1

RESULTS AND DISCUSSION The synthesis of dichlorobis(ethylenediamine)cobalt(III) chloride hydrochloride utilized hydrogen peroxide for the oxidation of CoCl2. The overall reaction followed the sequence: 4 Co3+ (aq) + 2 H2O 4 Co2+ (aq) + 4 H+ (aq) + O2 (g) 4 CoCl2 + 8 NH2CH2CH2NH2 + 2 H2O2 + 4 HCl 4 trans-[Co(en)2Cl2]Cl The cis product consists of two ethylenediamine bridges, which cross-over and give the molecule its chirality. The cis isomer has the two chlorine substituents on the same side and is optically active, while the trans isomer is not, as it has a mirror plane through the central atoms and can be superimposed on its mirror image, implying an axis of improper rotation. In fact, any Sn (improper rotation) axis implies achirality, and one is found in the trans isomer of dichlorobis(ehtylenediamine)cobalt(III) chloride.1 The trans isomer is converted to cis by concentrating a boiling solution of the former. This is because the cis isomer is less soluble. The change is marked by a change of color from green to violet.

Figure 2: cis-Diclorobis(ethylenediamine)cobalt(III) chloride

Figure 3: trans-Dichlorobis(ethylenediamine)cobalt(III) chloride

Tetrakis(triphenylphosphine)platinum(0) has platinum as the central atom with an oxidation state of zero. Platinum complexes are usually of either square-planar or the highly symmetric octahedral geometry. The reason platinum has an oxidation of zero in this complex is due to the low oxidation state of its ligands, tertiary phosphines. In the complex platinum has a d10 electron configuration, made by reaction of K2PtCl4 with KOH as the reducing agent. The coordination complex is of tetrahedral geometry. The reaction follows the overall sequence: K2[PtCl4] + 2KOH + 4[P(C6H5)3] + C2H5OH Pt(PPh3)4 + 4 KCl + CH3CHO + 2 H2O

Figure 4: Tetrakis(triphenylphosphine)platinum(0)

Dichloro(dipyridine)platinum(II) complexes have platinum as the central metal with a d8 configuration and have square-planar geometry, which is common for 4d and 5d series metals.1 According to the ligand field theory, the electrons in the complex fill the dz2 and t2g orbitals and there is destabilization in the xy plane. While d8 configurations give rise to both tetrahedral and square-planar geometries, the former does not have cis and trans isomers. In the reaction there is an SN2 like transition state intermediate with trigonal-bipyrimidal geometry. The overall reaction follows the sequence: K2PtCl4 + 2 C5H5N cis-[Pt(C5H5N)2Cl2] + 2 KCl cis-[Pt(C5H5N)2Cl2] + 2 C5H5N [Pt(C5H5N)4]Cl2 [Pt(C5H5N)4]Cl2 + 2 HCl trans-[Pt(C5H5N)2Cl2] + 2 C5H5N.HCl

Figure 5: cis-Dichloro(dipyridine)platinum(0)

Figure 6: trans- Dichloro(dipyridine)platinum(0)

EXPERIMENTAL trans-Dichlorobis(ethylenediamine)cobalt(III) Chloride Hydrochloride. Cobalt(II) chloride hexahydrate (1.0 g, 4.20 mmol) was dissolved in water (2.5 mL). A soln of ethylenediamine (4 mL, 10%) was added to the mixture and stirred for 10 min. Hydrogen peroxide (1.6 mL, 30%) was added to the soln dropwise with stirring, and stirred for 15 min. Conc HCl (3 mL) was added and the reaction mixture was heated in a water bath for 50 min until the color changed from purple to dark green. The resulting crystals were filtered by suction filtration and washed with cold methanol (5 mL). The final product, transdichlorobis(ethylenediamine)cobalt(III) chloride hydrochloride was dried and weighed (0.8001 g, 3.26 mmol, 78% yield). cis- Dichlorobis(ethylenediamine)cobalt(III) Chloride. transDichlorobis(ethylenediamine)cobalt(III) chloride hydrochloride (0.1002 g, 0.35 mmol) dissolved in saturated aq sodium bicarbonate (2 drops) and stirred. The reaction mixture was allowed to sit for 10 min. The crystals turned from green to purple. The soln was heated to dryness resulting in the product, cis- dichlorobis(ethylenediamine)cobalt(III) chloride (0.1005 g, 0.35 mmol). Tetrakis(triphenylphosphine)platinum(0). Triphenylphospine (300 mg, 1.14 mmol) was dissolved in hot absolute ethanol (2 mL) with stirring. Potassium hydroxide (30 mg, 0.053 mmol) was dissolved in a mixture of ethanol (700 L) and water (150 L) and added to the previous soln with stirring. Potassium tetrachloroplatinate(II) (105 mg, 0.24 mmol) was dissolved in water (1 mL) and added dropwise to the soln with stirring. After ~20 min a pale yellow precipitate formed. The soln was cooled to RT and recovered by suction filtration, washed with cold water (0.5 mL) followed by cold ethanol (0.5 mL) and allowed to dry. This yielded the product, tetrakis(triphenylphosphine)platinum(0) (0.6811 g, 0.55 mmol). cis-Dichloro(dipyridine)platinum(II). Potassium tetrachloroplatinate(II) (100 mg, 0.24 mmol) was dissolved in water (1 mL) and stirred at RT. Distilled pyridine (40 L, 0.5 mmol) in water (250 L) was added to the soln carefully with stirring. After a few minutes a light yellow precipitate started to form. Stirring was continued for 1 hr and the soln was cooled in an ice bath for 30 min. The crystals were collected by suction filtration and washed three times with ice water (0.5 mL) resulting in the final product, cis-dichloro(dipyridine)platinum(II) (0.0791 g, 0.19 mmol, 79% yield). trans- Dichloro(dipyridine)platinum(II). cis-Dichloro(dipyridine)platinum(II) (0.0791 g, 0.19 mmol) was dissolved in a solution of distilled pyridine (0.5 mL) and water (1 mL). The soln was heated and stirred just below the bp. The soln was heated to dryness. Conc HCl (1 mL) was added to the white residue and heated again to dryness, resulting in a pale yellow solid. The crystals were collected under suction filtration and washed with three portions of ice water (0.5 mL), then ethanol (1 mL) and finally ether (1 mL). The product, transdichloro(dipyridine)platinum(II) was allowed to dry (0.0474 g, 0.11 mmol, 58% yield).

CONCLUSION Coordination compounds are largely governed by their electronic configurations, as well as molecular symmetry. Chirality is observed in coordination compounds as well as follows the criterion of the absence of an axis of improper rotation. Octahedral complexes, such as dichlorobis(ehtylenediamine)cobalt(III) chloride have cis and trans isomers. However, the presence of both isomers doesnt imply that they are both optically active, as only the cis isomer is which can been seen by the structure. Platinum can form complexes with zero oxidation states, as well as tetrahedral, octahedral, and square-planar geometries. These complexes are important intermediates for other compounds and display the utility of platinum coordination compounds. Coordination compounds give rise to geometric isomers due to the exact position of the ligands around the central atom. Some positions and isomers are favored due to stability, but with influence the ligands can be repositioned to form other isomers, which can change the properties of the complexes.

REFERENCES (1) Atkins, P. Inorganic Chemistry, 4th Edition; W.H. Freeman and Co.: New York, 2006, pp 219-233