Transition Metal Catalysis

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Experiment 5: Transition Metal Catalysis 1. Introduction This experiment aims to utilize transition metal palladium catalyst for diarylacetylenes synthesis. In general, the procedures consist of two steps: the synthesis of catalyst precursor for active species Pd(PPh3)4 and the preparation of alkyne. Bases on the previous studies, there are two well-known reactions to synthesize diarylacetylenes. The first method discovered by Castro involves the use of copper acetylides. These reagents are prepared by treatment of an aqueous ammonia solution of cuprous iodide with an ethanol solution of monosubstituted aryl acetylenes. (eq.1) (1) The cuprous acetylides are then treated with aryl iodides in refluxing pyridine under nitrogen atmosphere to stoichiometrically generate diaryl acetylenes. (eq. 2) (2) By using amines as solvents and CuI as a co-catalyst, the method was improved to enable introducing alkyl substitutent to the triple bond at room temperature. The second method, which was used in this experiment, was introduced by Cassar and Heck by utilizing palladium complex to catalyze the reaction. (eq. 3) (3) 2. Experimental Section 2.1 The Catalytic Precursor Preparation A mixture of palladous chloride (0.0384 g, 0.216 mmol) and sodium chloride (0.0303 g, 0.518 mmol) in water (1.5 ml) was stirred and warmed to about 50ºC. The solution was allowed to cool down. A solution of triphenylphosphine (0.1280 g, 0.488 mmol) in ethanol (20 ml) was then prepared. The palladous chloride solution was added dropwise to the triphenylphosphine solution and stirred simultaneously. The resultant slurry was then warmed to about 50ºC over 30 minutes to coagulate the precipitate. The mixture was cooled, filtered, and washed with water, acetone, and ether. The product was dried in a 50ºC oven for

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