Upon the consideration of chemistry platinum, it is seen that both pt(II) and pt (iV)
occur frequently. Pt (II) compound are usually have a square planar geometry , whereas th pt (IV) comound are octahedrally co-ordinated. Contratry to many other metal compound, the platinum compound exhibit very slow ligand-exchange reaction. In fact this slow ligand exchange process is the origin that the cis and trans isomer of cisplatin are not interconverted in the solution. It has also been known for a long time that certain ligand-exchange reactions on Pt occur relatively faster than others. These relative reaction velocities can even be predicted from the so-called 'transeffect'. According to this rule, ligands in positions opposite (trans) to a certain ligand in a Pt(n)compound, are more or less rapidly exchanged compared to others. This has resulted in sequences of reactivity. For instance ligands trans to the following compounds in the sequence CN->fosfine>NO2->Br->CI->NH3>H20 are most easily replaced. This means that the ligands in the Ptcompounds in fact determine the reactivity. In addition to this trans effect rule, one should knowthat Ptamine ligand bonds [such as in Pt(NH3)22 or Pt(I,2-diaminoethane) 2 are usually very stable, whereas Pt-H20 bonds and Pt-CI bonds are rather labile) With these basic principles one can synthesize all kinds of c&- and trans-Pt compounds, and one can understand the reactions of the Pt compounds that occur in vivo
Preparation of cis-Diamminediiodoplatinum(II) 1. 25 mg of potassium tetrachloroplatinate (K2PtCl4). 2. 2. add 200 l of water and heat the solution with stirring in an oil bath to 40 oC. 3. Add a solution of 300 mg of KI in 500 l of warm water. (Upon addition the solution should change from red-brown to dark brown). Heat the mixture to 70 oC with continuous stirring. DO NOT OVERHEAT the solution! As soon as you reach 70 oC cool the mixture to room temperature. 4. Filter the solution using a Hirsch funnel to remove any solid impurities. (Use a few drops of water to make the transfer as quantitative as possible) 5. add 500 l of a 2.0M NH3 solution dropwise to the filtrate and stir. As soon as the ammonia is added, fine yellow crystals of cis-diamminediiodoplatinum(II)
6. 7. 8.
9.
should precipitate. If the supernatant liquid is still dark yellow in color, add a few more drops of ammonia to complete the reaction. Allow the beaker to stand for an additional 20 min at roomtemperature. Filter the yellow crystalline compound using a Hirsch funnel. Wash the product with 500 l ice-cold ethanol, followed by 1 ml ether (use these wash liquids to transfer as much as possible from the beaker to the filter). Air dry the compound and determine the percentage yield. Obtain the IR spectrum of the product.
Preparation of cis-Diamminedchloroplatinum(II), Cisplatin
1. 63 mg of silver sulfate in 10 ml of water. 2. Add 100 mg of the cisdiiodo derivative you prepared before, in SMALL PORTIONS, to this silver solution. (Note: The diiodo derivative might remain suspended at the surface of the solution. If this occurs, stir the solution vigorously with aspatula, making sure that all the compound is well wetted.) 3. Heat the suspension, with stirring on a sand bath (70-80 oC) for 10-12 min. Filter the mixture to separate the precipitate of AgI. 4. Concentrate the filtrate over an oil bath, while stirring, to ~2 ml. Treat this solution with 330 mg of KCl. Heat the mixture using an oil bath at 70-80 oC for 2-3 min. Bright yellow crystals of cisdiamminedichloroplatinum(II) should precipitate out. 5. The heating iscontinued for an additional 5-8 min. Cool the mixture to 0 oC in an icewater bath. 6. Filter the product using a Hirsch funnel. Wash the crystals with 500 l of ethanol followed by 1 ml of ether and dry them. 7. Determine the percentage yield. Obtain the IR spectra of the compound and compare it with your previous product.
