Where do you think the complex gets protonated? Where else could you have proton

Question

Where do you think the complex gets protonated? Where else could you have protonated the complex?

Protonation of [MnIV(salpn)(µ-O)]2

• Dissolve 0.1 mmol (70 mg) of [MnIV(salpn)(O)]2 in 200 mL of methylene chloride. Divide the solution into 4 equal portions. You may want to reserve a small amount of this solution (approx. 10 mL) for color comparison. For each of the following steps, be sure to make careful observations regarding the color of the solution. The best way to do this is to bring a little bit up in a pasteur pipette and use a flashlight (you may use your phone for this purpose) to aid in seeing the color of the solution.

• To one portion, add one equivalent of triflic acid (25 µL of 1.0 M solution in acetonitrile).

• To a second, add two equivalents triflic acid (50 µL of 1.0 M solution).

• Cool the two remaining portions to –78 °C in a dry ice/acetone bath, and add one equivalent triflic acid to one portion and two equivalents to the other. (Keep the flasks covered while cooling to avoid water condensation in the solutions.)

• Add 1 equivalent of triethylamine (7.2 M, so .025 mmol = 3.5 µL: For convenience, dilute 100 µL to 1 mL in acetonitrile and use 35 µL per equivalent) for each equivalent of triflic acid added to each solution above

Explanation / Answer

The complex, [MnIV(salpn)(µ-O)]2 is protonated by triflic acid as shown below

[MnIV(salpn)(µ-O)]2 + CF3SO3H ----- >  [MnIV(salpn)]2(µ-OH)(µ-O)(CF3SO3).

Protonated is done at the bridged Oxygen atom in the complex

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