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Typical Procedure for the Grignard Reactions of Bromoporphyrin Ni3 with Ketones or Aldehydes Freshly cut potassium (65 mg, 20 equiv, MgCl 2 (190 mg, 20 equiv, KI (275 mg, 20 equiv, and DME (10 mL) were placed in an oven-dried 50 mL Schlenk flask under N2. The mixture was stirred and heated to reflux for 2 h and cooled to r.t. A DME (20 mL) solution of Ni3 (50 mg, 1.0 equiv)and cyclohexanone (2a, 175 mL, 20 equiv) was then charged with a syringe slowly under N2. After 5 min, the mixture was diluted with CH2Cl2 (30 mL, quenched with sat. NH4Cl solution, and washed with H2O three times. The organic layer was passed through dry silica gel and evaporated to dryness. The resulting solid was purified by flash column chromatography (silica gel, 300-400 mesh, PE-CH2Cl2,1:1 v/v) to afford Ni4a 33 mg, 65% yield, Spectroscopy data of Ni4a are as follows
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+]: 700.1798; found: 700.1768.
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