Quadruply Metal-Metal Bonded Paddlewheels

1. Synthesis of Ligand ArN(H)C(H)NAr, Where Ar = p-(MeO)C₆H₄ (Figure 5)²

1. Combine 6.0 g (0.050 mol) of p-anisidine and 4.2 mL (0.025 mol) of triethylorthoformate in a 100 mL round bottom flask with a magnetic stir bar.
2. Attach a distillation head to the reaction flask.
3. With stirring, heat the reaction in an oil bath to reflux (120 °C). Once reflux is achieved, the byproduct ethanol should begin to distill from the reaction. Collect the ethanol in a beaker placed at the end of the distillation head.
4. Heat the reaction until the distillation of ethanol ceases (at least 1.5 h).
5. Remove the flask from the oil bath and allow the reaction mixture to cool to room temperature. A precipitate should form. If the product does not precipitate, place the flask in an ice bath and scratch the bottom of the flask with a spatula to encourage crystallization.
6. Recrystallize the product from a minimal amount of boiling toluene (for a more detailed procedure, please review the "Purifying Compounds by Recrystallization" video in the Essentials of Organic Chemistry series).
7. Collect the product by filtration through a fritted funnel and wash with 10 mL of hexanes.
8. Isolate the white product and allow it to dry in the air.
9. Collect a ¹H NMR of the solid using CDCl₃.

Figure 5. Synthesis of ArN(H)C(H)NAr, where Ar = p-MeOC₆H₄.

2. Setup of the Schlenk Line

NOTE: For a more detailed procedure, please review the "Schlenk Lines Transfer of Solvent" video in the Essentials of Organic Chemistry series. Schlenk line safety should be reviewed prior to conducting this experiment. Glassware should be inspected for star cracks before use. Care should be taken to ensure that O₂ is not condensed in the Schlenk line trap if using liquid N₂. At liquid N₂ temperature, O₂ condenses and is explosive in the presence of organic solvents. If it is suspected that O₂ has been condensed or a blue liquid is observed in the cold trap, leave the trap cold under dynamic vacuum. Do NOT remove the liquid N₂ trap or turn off the vacuum pump. Over time the liquid O₂ will sublime into the pump; it is only safe to remove the liquid N₂ trap once all of the O₂ has sublimed.

1. Close the pressure release valve.
2. Turn on the N₂ gas and the vacuum pump.
3. As the Schlenk line vacuum reaches its minimum pressure, prepare the cold trap with either liquid N₂ or dry ice/acetone.
4. Assemble the cold trap.

3. Synthesis of Mo₂(ArNC(H)NAr)₄ (Figure 6)²

CAUTION: The molybdenum source used in the synthesis of Mo₂(ArNC(H)NAr)₄ is Mo(CO)₆, which is highly toxic and may be fatal if inhaled, absorbed through the skin, or swallowed. CO is generated during the reaction. Therefore, the synthesis must be conducted in a well-ventilated hood.

1. Use standard Schlenk line techniques for the synthesis of Mo₂(ArNC(H)NAr)₄ (see the "Synthesis of a Ti(III) Metallocene Using Schlenk line Technique" video).
2. Add 0.34 g (1.3 mmol) Mo(CO)₆ and 1.0 g (3.9 mmol) of ArN(H)C(H)NAr to a 100 mL Schlenk flask and prepare the Schlenk flask for the cannula transfer of solvent.
3. Add 20 mL of degassed o-dichlorobenzene to the Schlenk flask via cannula transfer.
4. Fit the Schlenk flask with a condenser connected to the N₂ gas line.
5. Reflux the reaction for 2 h (180 °C) in a silicone-oil bath.
   NOTE: Mo(CO)₆ is volatile and will condense on the sides of the Schlenk flask during the reaction. To obtain higher yields, periodically re-dissolve any sublimed Mo(CO)₆ by pulling the flask out of the oil bath and gently swirling the solvent in the flask.
6. Remove the Schlenk flask from the oil bath and allow the mixture to cool to room temperature.
7. Filter the brown solution through a fritted funnel and wash the yellow precipitate with 10 mL of hexanes, followed by 5 mL of reagent grade acetone. The Mo₂(ArNC(H)NAr)₄ does decompose slowly in solution when O₂ is present. Therefore, the filtration should be done promptly once the reaction is removed from N₂.
8. Collect the solid yellow Mo₂(ArNC(H)NAr)₄ and allow it to air dry.
9. Using CDCl₃ measure the ¹H NMR spectrum of the product.

Figure 6. Synthesis of Mo₂(ArNC(H)NAr)₄, where Ar = p-MeOC₆H₄.

4. Single Crystal Growth

NOTE: Mo₂(ArNC(H)NAr)₄ oxidizes slowly in solution. The crystallization solvent should be degassed before use, but rigorous air-free conditions are not necessary to obtain X-ray quality crystals for single crystal X-ray diffraction.

1. Degas 10 mL of dichloromethane (CH₂Cl₂) by bubbling N₂ gas through the solution for 10 min (see the "Synthesis of a Ti(III) Metallocene Using Schlenk line Technique" video for a more detailed procedure on purging liquids).
2. Make a saturated solution of Mo₂(ArNC(H)NAr)₄ by dissolving 20 mg of the solid in 2 mL of the degassed CH₂Cl₂.
3. Make a pipette Celite plug by inserting a small piece of Kimwipe into a pipette. Add a small amount of Celite to the pipette.
4. Filter the CH₂Cl₂ solution through the pipette Celite plug into a small 5 mL vial. Help to push the solution through the Celite using a pipette bulb.
5. Using tweezers, insert the 5 mL vial into a 10 mL scintillation vial.
6. In the outer scintillation vial, add 2 mL of hexanes.
7. Tightly cap the scintillation vial and place it on a shelf where it will be undisturbed.
8. Allow at least 24 h for single crystal growth (see the "X-ray Crystallography" video in the Essentials of Organic Chemistry series for a more detailed procedure on how to grow single crystals).
9. Collect single crystal X-ray data on the sample (see the "Single Crystal and Powder X-ray Diffraction" video for a more detailed procedure on how to collect X-ray data).