cobalt(2+);diacetate;tetrahydrate

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

Procedure: A cobalt solution was obtained by dissolving cobalt acetate tetrahydrate (CoAc.4H2O, 4 g) in ethylene glycol (36 g) to produce a cobalt glycolate solution containing 10% cobalt acetate tetrahydrate. After stirring for 60 minutes, large particles dissolved, it became uniform red purple solution. A portion (9 g) of the cobalt acetate tetrahydrate solution and 1 g of a phosphoric acid solution (10% H3PO4 in ethylene glycol) were mixed in an open glass beaker. After shaking, flocculates in dark bluish purple formed in the bottom of the glass beaker. After 10 days, top 3 ml was red liquid mainly ethylene glycol, bottom 7 ml was dark purple flocculates.

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

Procedure: Indicator compositions were prepared as for Example 11. The colorants used are listed in Table 13. The second solution (Indicator Composition 13) was prepared by adding 1.0 g of cobalt(II) acetate tetrahydrate {Co(C2H3O2)2.4H2O} (available from Sigma-Aldrich Fine Chemicals, St. Louis, Mo.) to 13 ml of water. Devices were prepared and tested as described in Example 11. The results are recorded in Table 13. Indicator compositions were prepared as for Example 11 The second solution (Indicator Composition 13) was prepared Devices were prepared

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

Procedure: To a stirred solution of ‘salen’ ligand (7e) (43 mg, 0.045 mmol, 1 equiv.) in 5 mL CH2Cl2, a methanolic (2 mL) solution of cobalt (II) acetate tetrahydrate (11.4 mg, 45 μmol, 1.0 equiv.), was added via cannula, under Ar. The Co(II)-salen complex precipitated out as a red solid. After filtration, the Co(II) complex was taken up in CH2Cl2 or toluene (2 mL) and stirred with acetic acid (>10 equiv.) or 3,5-dinitrobenzoic acid (1 equiv.) open to the air. The oxidation was followed by TLC, formation of a greenish-brown spot of lower Rf {Co-(III) complex} from the visibly red, higher Rf spot characteristic of the Co-(II) salen. When TLC indicated the completion of the reaction (2-12 h), the solvent was evaporated, and the Co(III)-salen complex further dried in vacuo. The Co(III) carboxylate complexes so prepared were used for HKR experiments, under ISES (bilayer) conditions or under neat ‘Jacobsen’ (conventional) conditions. The Co(II)-salen complex precipitated out as a red solid After filtration the completion of the reaction (2-12 h) the solvent was evaporated the Co(III)-salen complex further dried in vacuo The Co(III) carboxylate complexes so prepared

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

Procedure: To a stirred solution of ‘salen’ ligand (7e) (43 mg, 0.045 mmol, 1 equiv.) in 5 mL CH2Cl2, a methanolic (2 mL) solution of cobalt (II) acetate tetrahydrate (11.4 mg, 45 μmol, 1.0 equiv.), was added via cannula, under Ar. The Co(II)-salen complex precipitated out as a red solid. After filtration, the Co(II) complex was taken up in CH2Cl2 or toluene (2 mL) and stirred with acetic acid (>10 equiv.) or 3,5-dinitrobenzoic acid (1 equiv.) open to the air. The oxidation was followed by TLC, formation of a greenish-brown spot of lower Rf {Co-(III) complex} from the visibly red, higher Rf spot characteristic of the Co-(II) salen. When TLC indicated the completion of the reaction (2-12 h), the solvent was evaporated, and the Co(III)-salen complex further dried in vacuo. The Co(III) carboxylate complexes so prepared were used for HKR experiments, under ISES (bilayer) conditions or under neat ‘Jacobsen’ (conventional) conditions. The Co(II)-salen complex precipitated out as a red solid After filtration the completion of the reaction (2-12 h) the solvent was evaporated the Co(III)-salen complex further dried in vacuo The Co(III) carboxylate complexes so prepared

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

Procedure: Indicator compositions were prepared as for Example 11. The colorants used are listed in Table 13. The second solution (Indicator Composition 13) was prepared by adding 1.0 g of cobalt(II) acetate tetrahydrate {Co(C2H3O2)2.4H2O} (available from Sigma-Aldrich Fine Chemicals, St. Louis, Mo.) to 13 ml of water. Devices were prepared and tested as described in Example 11. The results are recorded in Table 13. Indicator compositions were prepared as for Example 11 The second solution (Indicator Composition 13) was prepared Devices were prepared

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

Procedure: Indicator compositions were prepared as for Example 11. The colorants used are listed in Table 13. The second solution (Indicator Composition 13) was prepared by adding 1.0 g of cobalt(II) acetate tetrahydrate {Co(C2H3O2)2.4H2O} (available from Sigma-Aldrich Fine Chemicals, St. Louis, Mo.) to 13 ml of water. Devices were prepared and tested as described in Example 11. The results are recorded in Table 13. Indicator compositions were prepared as for Example 11 The second solution (Indicator Composition 13) was prepared Devices were prepared

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

Procedure: The reaction was carried out in a glove box and solvents were degassed prior to use. The polymer 4 (95 mg, 0.16 mmol) was dissolved in dichloromethane (2 mL) in a vial charged with a stir bar. A solution of cobalt acetate tetrahydrate (49.8 mg, 0.20 mmol) in methanol (2 mL) was added slowly to the vial, resulting in precipitation of a red-brown powder. After the suspension was stirred at rt for 3 h, additional methanol (6 mL) was added to precipitate more solid. The solid was collected by filtration, washed with 1/10 dichloromethane/methanol (2×10 mL) and methanol (10 mL), and dried under high vacuum to give the desired product Co(II)(4) (99 mg, 95%). Using a similar procedure, Co(II)(2), Co(II)(3), Co(II)(5), Co(II)(6), and Co(II)(7) were synthesized. The reaction was carried out in a glove box solvents were degassed a vial charged with a stir bar resulting in precipitation of a red-brown powder to precipitate more solid The solid was collected by filtration washed with 1/10 dichloromethane/methanol (2×10 mL) and methanol (10 mL) dried under high vacuum

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,2'-thiobis(4-t-octylphenol) (44.2 g.) and anhydrous potassium carbonate (6.9 g.) was heated in refluxing 2-propanol for about 0.5 hr. and then cobalt (II) acetate tetrahydrate (12.5 g.) was added. The reaction mixture was stirred at reflux temperature for about 4 hr. during which a precipitate of pink solids was formed. The mixture was filtered and the solids were washed with water and dried. The solids were recystallized from 2-propanol and the resulting pink solid, m.p. 355°-357° C. was dealcoholated by heating at 140° C. at less than 0.1 mm of mercury to give the cobalt 2,2'-thiobis-(4-t-octylphenolate) as a brownish solid m.p. greater than 360° C. was heated at reflux temperature for about 4 hr during which a precipitate of pink solids was formed The mixture was filtered the solids were washed with water dried

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

Procedure: The reaction was carried out in a glove box and solvents were degassed prior to use. The polymer 4 (95 mg, 0.16 mmol) was dissolved in dichloromethane (2 mL) in a vial charged with a stir bar. A solution of cobalt acetate tetrahydrate (49.8 mg, 0.20 mmol) in methanol (2 mL) was added slowly to the vial, resulting in precipitation of a red-brown powder. After the suspension was stirred at rt for 3 h, additional methanol (6 mL) was added to precipitate more solid. The solid was collected by filtration, washed with 1/10 dichloromethane/methanol (2×10 mL) and methanol (10 mL), and dried under high vacuum to give the desired product Co(II)(4) (99 mg, 95%). Using a similar procedure, Co(II)(2), Co(II)(3), Co(II)(5), Co(II)(6), and Co(II)(7) were synthesized. The reaction was carried out in a glove box solvents were degassed a vial charged with a stir bar resulting in precipitation of a red-brown powder to precipitate more solid The solid was collected by filtration washed with 1/10 dichloromethane/methanol (2×10 mL) and methanol (10 mL) dried under high vacuum

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,2'-thiobis(4-t-octylphenol) (44.2 g.) and anhydrous potassium carbonate (6.9 g.) was heated in refluxing 2-propanol for about 0.5 hr. and then cobalt (II) acetate tetrahydrate (12.5 g.) was added. The reaction mixture was stirred at reflux temperature for about 4 hr. during which a precipitate of pink solids was formed. The mixture was filtered and the solids were washed with water and dried. The solids were recystallized from 2-propanol and the resulting pink solid, m.p. 355°-357° C. was dealcoholated by heating at 140° C. at less than 0.1 mm of mercury to give the cobalt 2,2'-thiobis-(4-t-octylphenolate) as a brownish solid m.p. greater than 360° C. was heated at reflux temperature for about 4 hr during which a precipitate of pink solids was formed The mixture was filtered the solids were washed with water dried

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

Procedure: A cobalt solution was obtained by dissolving cobalt acetate tetrahydrate (CoAc·4H2O, 4 g) in ethylene glycol (36 g) to produce a cobalt glycolate solution containing 10% cobalt acetate tetrahydrate. After stirring for 60 minutes, large particles dissolved, it became uniform red purple solution. A portion (9 g) of the cobalt acetate tetrahydrate solution and 1 g of a phosphoric acid solution (10% H3PO4 in ethylene glycol) were mixed in an open glass beaker. After shaking, flocculates in dark bluish purple formed in the bottom of the glass beaker. After 10 days, top 3 ml was red liquid mainly ethylene glycol, bottom 7 ml was dark purple flocculates.

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

Procedure: Indicator compositions were prepared as for Example 11. The colorants used are listed in Table 13. The second solution (Indicator Composition 13) was prepared by adding 1.0 g of cobalt(II) acetate tetrahydrate {Co(C2H3O2)2.4H2O} (available from Sigma-Aldrich Fine Chemicals, St. Louis, Mo.) to 13 ml of water. Devices were prepared and tested as described in Example 11. The results are recorded in Table 13. Indicator compositions were prepared as for Example 11 The second solution (Indicator Composition 13) was prepared Devices were prepared