38465-86-0/1，5-環(huán)辛二烯雙(甲基聯(lián)苯基磷化氫)銥六氟磷酸鹽的應用

背景及概述^[1]

1，5-環(huán)辛二烯雙(甲基聯(lián)苯基磷化氫)銥六氟磷酸鹽簡稱[Ir(cod)(PMePh₂)₂] PF₆，是一種銥金屬催化劑。有文獻報道其可與2,2-聯(lián)吡啶進一步反應生成另一種銥金屬催化劑[Ir(bipy)H₂(PRPh₂)₂] PF₆。

應用^[1-2]

[Ir(cod)(PMePh₂)₂] PF₆制備[Ir(bipy)H₂(PRPh₂)₂] PF₆的方法如下：

將[Ir(cod)(PMePh₂)₂] PF₆（1當量，286.3 mg，0.338 mmol）和2,2-聯(lián)吡啶（1當量，53.0 mg，0.338 mmol）溶解在脫氣的CH₂Cl₂（10 mL）中。將所得紅色溶液冷卻至0℃。在不斷攪拌下鼓入二氫氣體20分鐘。 向橙色溶液中滴加二乙醚（100mL）以沉淀出250.9mg的米色固體（82.9％），將其通過真空過濾獲得，并真空干燥。用CH₂Cl₂/Et₂O進行重結(jié)晶。

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%.

報道二、

Albinati A等人報道了[Ir(cod)(PMePh₂)₂] PF₆可進一步制備[(eta5-C5H5)M(mu-H)2(mu-(eta5:eta1-C5H4))IrH(PMePh₂)₂][BPh₄] (M = Mo and W)。

參考文獻

[1] Macchioni A , Zuccaccia C , Clot E , et al. Selective Ion Pairing in [Ir(bipy)H2(PRPh2)2]A (A = PF6, BF4, CF3SO3, BPh2, R = Me, Ph): Experimental Identification and Theoretical Understanding[J]. Organometallics, 2001, 20(11):2367-2373.

[2]Albinati A , Togni A , Venanzi L M . Cationic molybdenum(IV)- and tungsten(IV)-iridium(III) complexes with hydride and eta5:eta1-cyclopentadienyl bridging ligands. Syntheses and x-ray crystal structure of [(eta5-C5H5)M(mu-H)2(mu-(eta5:eta1-C5H4))IrH(PMePh2)2][BPh2] (M = Mo and W)[J]. Organometallics, 1986, 5(9):1785-1791.