Application of 1,5-cyclooctadiene bis(methylbiphenylphosphine)iridium hexafluorophosphate_Industrial additives

Background and overview^[1]

1,5-Cycloctadiene bis(methylbiphenylphosphine)iridium hexafluorophosphate abbreviation [Ir(cod)(PMePh₂)₂] PF₆, is an iridium metal catalyst. There are reports in the literature that it can further react with 2,2-bipyridine to form another iridium metal catalyst [Ir(bipy)H₂(PRPh₂) ₂] PF₆.

Apply^[1-2]

[Ir(cod)(PMePh₂)₂] PF₆ Preparation of [Ir(bipy)H₂ sub>(PRPh₂)₂] The method of PF₆ is as follows:

Combine [Ir(cod)(PMePh₂)₂] PF₆ (1 equivalent, 286.3 mg, 0.338 mmol) and 2 ,2-bipyridine (1 equiv, 53.0 mg, 0.338 mmol) was dissolved in degassed CH₂Cl₂ (10 mL). The resulting red solution was cooled to 0°C. Dihydrogen gas was bubbled in with constant stirring for 20 minutes. Diethyl ether (100 mL) was added dropwise to the orange solution to precipitate 250.9 mg of beige solid (82.9%), which was obtained by vacuum filtration and dried under vacuum. Recrystallize with CH₂Cl₂/Et₂O.

¹H NMR (CD₂Cl₂, 298 K): δ H (ppm) 8.46 (dd, 3J2,3 = 5.4, ​​5J2,5 = 0.7, 2), 7.93 (d, 3J5,4 = 8.0, 5), 7.87 (ddd, 3J4,3 = 7.5, 3J4,5 = 8.2, 4J4,2 = 1.5, 4), 7.33 (m, p), 7.25 (m, o and m), 7.08 (ddd, 3J3,4 = 7.1, 3J3,2) 5.5, 4J3,5 = 1.4, 3), 1.88 (t Harris,17b |2JH,P + 4JH,P| = 6.4, PMePh2), -19.87 (t, 2JH,P = 16.8, H). ¹³C{¹H} NMR (CD2Cl2, 298 K): δ C (ppm) 155.9 (s, 6), 155.4 (s, 2), 137.5 (s, 4), 133.4 (t, 1Jipso,P = 26.7, ipso), 132.0 (t, 2Jo,P = 6.0, o), 130.5 (s, p), 128.7 (t, 3Jm,P = 5.0, m), 127.5 (s, 3), 123.8 (s, 5), 17.0 (t, |1JC,P + 3JC, P| = 37.6, PMePh2). ³¹P{¹H} NMR (CD₂Cl₂, 298 K): δ P (ppm) -0.27 (s, PMePh2), -143.14 (sept, 1JP,F = 711.0, PF6 -). ¹⁹F NMR (CD₂Cl₂, 298 K): δ F (ppm) -73.50 (d,1JF,P = 711.0, PF6 -). IR (thin film, cm^-1 ): ν(Ir-H) 2176.1, ν(PF6) 836.2. Anal. Calcd for C36H36IrN2P3F6: C, 44.62; H, 3.84; N, 2.74. Found: C, 44.58; H, 4.14; N, 2.75. Yield: 82.9%.

Report 2,

Albinati A et al. reported that [Ir(cod)(PMePh₂)₂] PF₆ can be further prepared [(eta5- C5H5)M(mu-H)2(mu-(eta5:eta1-C5H4))IrH(PMePh₂)₂][BPh₄] (M = Mo and W).