(1,5-Cyclooctadiene)(methoxy)iridium(I) Dimer

Used Chemicals

• Benzo[1,2-b:4,5-b']dithiophene [B3464]
• (1,5-Cyclooctadiene)(methoxy)iridium(I) Dimer (= [Ir(cod)OMe]₂) [C2662]
• 4,4'-Di-tert-butyl-2,2'-bipyridyl (= dtbpy) [D3134]
• Bis(pinacolato)diboron (= (pinB)₂) [B1964]
• Cyclohexane

Procedure

A solution of dtbpy (27 mg, 0.05 mmol), bis(pinacolato)diboron (1.0 g, 4.0 mmol) and [Ir(cod)OMe]₂ (33 mg, 0.025 mmol) in cyclohexane (40 mL) was stirred under nitrogen at room temperature for 10 min. Benzo[1,2-b:4,5-b']dithiophene (380 mg, 2.0 mmol) was added the mixture and stirred 80 ˚C for 18 hours. The reaction mixture was quenched with water and separated both layers, extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and filtered. The solvent was removed under reduced pressure and the crude was washed with methanol (20 mL) to give 1 as a white solid (0.771 g, 87% yield).

Experimenter’s Comments

The reaction mixture was monitored by NMR.
Cyclohexane was bubbled with nitrogen before use.

Analytical Data

Compound 1

¹H NMR (270 MHz, CDCl₃); δ 8.36 (s, 2H), 7.90 (s, 2H), 1.39 (s, 24H).

Lead Reference

• Synthesis and Transistor Application of Bis[1]benzothieno[6,7‑d:6′,7′‑d′]benzo[1,2‑b:4,5‑b′]dithiophenes
  • S. Nishinaga, H. Mori, Y. Nishihara. J. Org. Chem. 2018, 83, 5506.

Reference

• Room temperature borylation of arenes and heteroarenes using stoichiometric amounts of pinacolborane catalyzed by iridium complexes in an inert solvent
  • T. Ishiyama, Y. Nobuta, J. F. Hartwig, N. Miyaura, Chem. Commun. 2003, 2924.

References

• E. M. Simmons, J. F. Hartwig, Nature 2012, 483, 70.