palladium(2+);diacetate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The procedure of Example 6 was followed except that the reaction mixture was made up of 0.2 g. of palladium sponge, 42 g. of glacial acetic acid and 2 drops of distilled water. The reaction temperature was from 65°-70° C. and NO was bubbled slowly through the mixture under these conditions over a 20-25 minute period, during this time the mixture was periodically flushed with oxygen. All the palladium sponge dissolved during this time to give an orange-red solution which upon concentration afforded orange-red crystals of trimeric palladium acetate in 95% yield. The crystals were soluble in benzene and toluene and showed a sharp infrared band at 1600 cm-1. was from 65°-70° C. NO was bubbled slowly through the mixture under these conditions over a 20-25 minute period, during this time the mixture was periodically flushed with oxygen All the palladium sponge dissolved during this time to give an orange-red solution which upon concentration

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Palladium diacetate was prepared from palladium sponge, acetic acid and HNO2 by adding 0.295 g. of palladium sponge and 45 ml. of glacial acetic acid in the apparatus described in example 1. The resulting mixture was stirred at ambient temperature for about 2 hours with an occasional addition of gaseous HNO2 to the mixture. The mixture was stirred overnight at ambient temperature and was then heated to 115° C. for one hour while being purged with argon. The resulting brown-red solution was filtered and the filtrate was concentrated to yield orange-red crystals of trimeric, hydrocarbon-soluble palladium diacetate in 96% yield. by adding 0.295 g was then heated to 115° C. for one hour while being purged with argon The resulting brown-red solution was filtered the filtrate was concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: All raw materials were technical grade without any further purification. A solution of 5.0 gm [27.7 millimoles (mmol)]of 1,10-phenanthroline dissolved in 250 ml of benzene was added dropwise with stirring to a solution of 4.0 gm of palladium diacetate (17.8 mmol) in 250 ml of benzene at room temperature. A bright yellow solid precipitated from the solution. After 3 hours the solid was isolated by filtration. The precipitate was washed with 200 ml of benzene, and 400 ml of petroleum ether and then dried at reduced pressure overnight. The yield of pale yellow solid was 7.20 g (17.8 mmol; 100%). without any further purification was added dropwise A bright yellow solid precipitated from the solution After 3 hours the solid was isolated by filtration The precipitate was washed with 200 ml of benzene, and 400 ml of petroleum ether dried at reduced pressure overnight

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: All raw materials were technical grade without any further purification. A solution of 5.0 gm [27.7 millimoles (mmol)]of 1,10-phenanthroline dissolved in 250 ml of benzene was added dropwise with stirring to a solution of 4.0 gm of palladium diacetate (17.8 mmol) in 250 ml of benzene at room temperature. A bright yellow solid precipitated from the solution. After 3 hours the solid was isolated by filtration. The precipitate was washed with 200 ml of benzene, and 400 ml of petroleum ether and then dried at reduced pressure overnight. The yield of pale yellow solid was 7.20 g (17.8 mmol; 100%). without any further purification was added dropwise A bright yellow solid precipitated from the solution After 3 hours the solid was isolated by filtration The precipitate was washed with 200 ml of benzene, and 400 ml of petroleum ether dried at reduced pressure overnight

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into 12 mL of dry DMF in an oven dried, nitrogen filled tube was placed M (3.0 g, 15 mmol), 1-iodo-3-bromobenzene (1.6 mL, 13 mmol), palladium(II)acetate (0.42 g, 1.9 mmol), tetrabutylammoniumchloride (3.5 g, 13 mmol), and solid NaHCO3 (2.6 g, 31 mmol). The tube was sealed and heated to 80° C. for 16 hours. The cooled reaction mixture was diluted with EtOAc, passed through a small plug of silica gel to remove the catalyst, and extracted 2× with brine. The solution was then dried over Na2SO4, concentrated, and purified by flash chromatography eluting with 2:1 and 1:1 heptane: EtOAc to afford N (1.8 g, 5 mmol, 40%) (MS;M+H: 356.1, 358.1). Likewise N′ was formed (0.92 g, 3.1 mmol, 77%) (MS;M+H: 293.2) from M (1.0 g, 5 mmol), 3-iodoaniline (0.5 mL, 4.2 mmol), Pd(OAc)2 (0.14 g, 0.62 mmol), Bu4NCl (1.16 g, 4.2 mmol), and NaHCO3 (0.87 g, 10 mmol) in 4 mL of dry DMF. Into 12 mL of dry DMF in an oven dried nitrogen filled tube was placed The tube was sealed The cooled reaction mixture to remove the catalyst extracted 2× with brine The solution was then dried over Na2SO4 concentrated purified by flash chromatography eluting with 2:1 and 1:1 heptane EtOAc to afford N (1.8 g, 5 mmol, 40%) (MS;M+H: 356.1, 358.1)

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of the catalyst was prepared as follows: An oven-dried Wheaton vial equipped with a magnetic stir bar was charged with Pd(OAc)2 (5.60 mg, 0.025 mmol, 1.0 eq.) and 2-dicyclohexylphosphino-2′.4′,6′-tri-iso-propyl-1,1′-biphenyl (4c) (24.5 mg, 0.050 mmol, 2.0 eq.). Toluene (3.0 mL) was added and the vial was sealed with a PTFE-lined plastic cap. The resulting mixture was stirred at 23° C. for 1 h to yield a reddish Pd/4c catalyst solution (0.00833 N Pd in toluene). A solution of the catalyst was prepared An oven-dried Wheaton vial equipped with a magnetic stir bar

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of the catalyst was prepared as follows: A 20 mL Wheaton vial equipped with a magnetic stir bar was charged with Pd(OAc)2 (5.60 mg, 0.025 mmol, 1.0 eq.) and 2-dicyclohexylphosphino-2′.4′,6′-tri-iso-propyl-1,1′-biphenyl (4c) (24.5 mg, 0.050 mmol, 2.0 eq.). Toluene (3.0 mL) was added and the vial was sealed with a PTFE-lined plastic cap. The resulting mixture was stirred at 23° C. for 1 h to yield a reddish Pd/4c catalyst solution (0.00833 N Pd in toluene). A solution of the catalyst was prepared A 20 mL Wheaton vial equipped with a magnetic stir bar

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of the catalyst was prepared as follows: A 20 mL Wheaton vial equipped with a magnetic stir bar was charged with Pd(OAc)2 (5.60 mg, 0.025 mmol, 1.0 eq.) and 2-dicyclohexylphosphino-2′.4′,6′-tri-iso-propyl-1,1′-biphenyl (4c) (24.5 mg, 0.050 mmol, 2.0 eq.). Toluene (3.0 mL) was added and the vial was sealed with a PTFE-lined plastic cap. The resulting mixture was stirred at 23° C. for 1 h to yield a reddish Pd/4c catalyst solution (0.00833 N Pd in toluene). A solution of the catalyst was prepared A 20 mL Wheaton vial equipped with a magnetic stir bar

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of the catalyst was prepared as follows: A 20 mL Wheaton vial equipped with a magnetic stir bar was charged with Pd(OAc)2 (5.60 mg, 0.025 mmol, 1.0 eq.) and 2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′-biphenyl (4d) (20.5 mg, 0.050 mmol, 2.0 eq.). Toluene (3.00 mL) was added and the vial was sealed with a PTFE-lined plastic cap. The resulting mixture was stirred at 23° C. for 45 min. resulting in a yellow Pd/4d catalyst solution (0.00833 N Pd in toluene). A solution of the catalyst was prepared A 20 mL Wheaton vial equipped with a magnetic stir bar

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of the catalyst was prepared as follows: An oven-dried Wheaton vial equipped with a magnetic stir bar was charged with Pd(OAc)2 (5.60 mg, 0.025 mmol, 1.0 eq.) and 2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′-biphenyl (4d) (20.5 mg, 0.050 mmol, 2.0 eq.). Toluene (3.00 mL) was added and the vial was sealed with a PTFE-lined plastic cap. The resulting mixture was stirred at 23° C. for 45 min. resulting in a yellow Pd/4d catalyst solution (0.00833 N Pd in toluene). A solution of the catalyst was prepared An oven-dried Wheaton vial equipped with a magnetic stir bar

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of the catalyst was prepared as follows: An oven-dried Wheaton vial equipped with a magnetic stir bar was charged with Pd(OAc)2 (5.60 mg, 0.025 mmol, 1.0 eq.) and 2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′-biphenyl (4d) (20.5 mg, 0.050 mmol, 2.0 eq.). Toluene (3.00 mL) was added and the vial was sealed with a PTFE-lined plastic cap. The resulting mixture was stirred at 23° C. for 45 min. resulting in a yellow Pd/4d catalyst solution (0.00833 N Pd in toluene). A solution of the catalyst was prepared An oven-dried Wheaton vial equipped with a magnetic stir bar

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into 40 ml of distilled trifluoroacetic acid was dissolved 1.0 g of palladium acetate. The solvent was distilled off and an additional 20 ml of trifluoroacetic acid was added and distilled off. The residual solid was dried in facuo at 40° C. to afford 1.3 g of brown product, i.e. palladium (II) trifluoroacetate, mp 210° C. (dec). The solvent was distilled off an additional 20 ml of trifluoroacetic acid was added distilled off The residual solid was dried in facuo at 40° C.