Preparation of Olefinic Complexes of Platinum(II) and Palladium(II)

By Daniel Rodman
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Abstract Platinum and palladium complexes are common in catalysis and form a wide variety of coordination compounds. The complexes synthesized in this experiment highlight bonding with alkenes and dienes, and are called complexes. The Dewar-Chatt-Duncanson model explains this type of bonding and states that alkenes bond to a metal atom with both carbons of the double bond equidistant from the metal, creating a cloud of high electron density in which the bond electrons donate to an empty d-orbital on the metal, forming a bond. The filled metal d-orbital donates electron density to the empty * orbital found on the alkene, which can form a bond. INTRODUCTION Platinum and palladium are group 10 transition metals that are used widely in catalysis, and studies on them help to understand catalytic intermediates. Coordination complexes can form with alkenes in which both carbons of the double bond are the same distance away from the metal, in which the bonds seem to coordinate with the metal, rather than form bonds with one of the carbons. This is termed a complex. In complexes a transition metal forms a complex with an unsaturated molecule, in which electrons are donated from the filled orbital to an empty orbital in the metal. Likewise, a filled d-orbital can donate electrons to a * orbital on the alkene.1 RESULTS AND DISCUSSION The stability of alkene metal complexes is explained by the Dewar-Chatt-Duncanson model. It states that alkenes bond to a metal atom with both carbons of the double bond equidistant from the metal, creating a cloud of high electron density in which the bond electrons can donate to an empty d-orbital on the metal, forming a bond. Also, the filled metal d-orbital can donate electron density to the empty * orbital found on the alkene, which can form a bond.1 The electron donor and electron acceptor character are for the most part evenly balanced in some complexes with light or no substitution. When the alkene or alkyne is substituted with large or many substituents, it can alter the bond length and strength. It has been suggested that the flow of the electrons lowers the bond order of the coordinated alkene, resulting in a longer C=C coordinated bond length.2 Cyclooctadienylplatinum(II) dichloride was synthesized via the reduction of Pt(IV) with a cyclic olefin according to the following sequence: C8H12 + H2PtCl6(H2O)x (4-C8H12)PtCl2 In cyclooctadienylplatinum(II) dichloride the central platinum has square planar geometry, and the 1,5 cyclooctadiene ring shows symmetrical coordination to the metal.

Figure 1. Structure of Cyclooctadienylplatinum(II) dichloride.

However, the ethylene carbons have been shown to be slightly twisted to avoid eclipsing.2 . Di-chlorodichlorodiethylenedipalladium(II) was synthesized from dichlorobis(benzonitrile)palladium(II), which was made in the following sequence: PdCl2 + 2 C6H5CN Pd(C6H5CN)2Cl2 Triple bonds, as found in dichlorobis(benzonitrile)palladium(II) have the potential to donate four electrons, but when the bond is side on to only one metal atom it is considered a two electron donor.1 Di--chlorodichlorodiethylenedipalladium(II) is a special example in which each palladium atom coordinates with a bond on ethylene while sharing two chlorine atoms that form the bridge of the molecule.

Figure 2. Structure of 1 Di--chlorodichlorodiethylenedipalladium(II).

EXPERIMENTAL Cyclooctadienylplatinum(II) dichloride. Hydrated chloroplatinic acid (100 mg, 0.24 mmol) was added to an 2rlenmeyer flask, along with glacial acetic acid (1.0 mL). The mixture was heated to ~75C in a water bath. 1,5-Cyclooctadiene (200 mg, 0.96 mmol) was added to the warm soln and swirled, then allowed to cool to RT. After cooling, water (500 L) was added and the dark soln was allowed to stand at RT for ~ 1hr. A greyish precipitate had formed and was filtered by vacuum filtration, and allowed to dry and weighed (0.0882 g, 0.236 mmol). Dichlorobis(benzonitrile)palladium(II). Palladium(II) chloride (130 mg, 0.73 mmol) was placed in a reaction tube along with benzonitrile (1 mL, 9.6 mmol). The mixture was heated gently with stirring until most of the PdCl2 had dissolved. The remaining insoluble material was removed via vacuum filtration. The filtrate was collected and allowed to cool to RT. To the cool filtrate, hexane (2 mL) was added. The solution was filtered by vacuum filtration and yellow crystals precipitated. The crystals were washed with hexane (1 mL), allowed to dry, and weighed (0.0153 g, 0.040 mmol, 5.5% yield).

Di--chlorodichlorodiethylenedipalladium(II). Dichlorobis(benzonitrile)palladium(II) (0.0153 g, 0.040 mmol) was placed in a reaction tube with toluene (2 mL) and a magnetic stirring bar. The mixture was stirred until dissolution was noticed. Insoluble material was removed via vacuum filtration and cyclohexene (2 mL) was added to the filtrate. The very small crystals were collected by vacuum filtration, yet they were stuck in the filter, and could not be weighed. CONCLUSION Coordination complexes can form with alkenes in which both carbons of the double bond are the same distance away from the metal, in which the bonds coordinate with the central metal atom. The Dewar-Chatt-Duncanson model describes this behavior in which the bond electrons donate to an empty d-orbital on the metal forming a bond, while the filled metal dorbital donates electron density to the empty * orbital on the alkene, which can form a bond. This type of coordination compound is termed a complex. The bonds are not the same length or strength as a regular C=C bond, and its properties vary depending on the alkene or diene and its substituents. REFERENCES 1) Atkins, P. Inorganic Chemistry, 4th Edition; W.H. Freeman and Co.: New York, 2006, pp 535-545 2) Syed, A.; Stevens, E. D.; Cruz, S. G. Reexamination of the Bonding in Dichloro( cycloocta- 1,5-diene)platinum. Inorg. Chem. 1984. 23(3673-3674)