38465-86-0/1，5-环辛二烯双(甲基联苯基磷化氢)铱六氟磷酸盐的应用

背景及概述^[1]

1，5-环辛二烯双(甲基联苯基磷化氢)铱六氟磷酸盐简称[Ir(cod)(PMePh₂)₂] PF₆，是一种铱金属催化剂。有文献报道其可与2,2-联吡啶进一步反应生成另一种铱金属催化剂[Ir(bipy)H₂(PRPh₂)₂] PF₆。

应用^[1-2]

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

将[Ir(cod)(PMePh₂)₂] PF₆（1当量，286.3 mg，0.338 mmol）和2,2-联吡啶（1当量，53.0 mg，0.338 mmol）溶解在脱气的CH₂Cl₂（10 mL）中。将所得红色溶液冷却至0℃。在不断搅拌下鼓入二氢气体20分钟。 向橙色溶液中滴加二乙醚（100mL）以沉淀出250.9mg的米色固体（82.9％），将其通过真空过滤获得，并真空干燥。用CH₂Cl₂/Et₂O进行重结晶。

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%.

报道二、

Albinati A等人报道了[Ir(cod)(PMePh₂)₂] PF₆可进一步制备[(eta5-C5H5)M(mu-H)2(mu-(eta5:eta1-C5H4))IrH(PMePh₂)₂][BPh₄] (M = Mo and W)。

参考文献

[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.