33394-11-5

Upstream product

• 881381-32-4 [IrHCl₂(triphenylphosphine)2(3-methylpyrazole)] 
• 7732-18-5 water 
• 536-74-3 phenylacetylene 
• 881381-20-0 [IrHCl₂(triphenylphosphine)2(pyrazole)] 
• 881381-24-4 [IrHCl₂(triphenylphosphine)2(imidazole)] 
• 16971-01-0 fac-IrHCl₂(PPh₃)3 
• 16971-01-0 mer-IrHCl₂(PPh₃)3 

Relevant academic research and scientific papers

Preparation and reactivity of iridium(III) hydride complexes with pyrazole and imidazole ligands

Pyrazole IrHCl2(HRpz)P2 [P = PPh3, P iPr3; R = H, 3-Me], bis(pyrazole) [IrHCl(HRpz) 2(PPh3)2]BPh4 and imidazole IrHCl2(HIm)(PPh3)2 derivatives were prepared by allowing the IrHCl2(PPh3)3 complex to react with the appropriate azole in refluxing 1,2-dichloroethane. Nitrile IrHCl 2(CH3CN)(PPh3)2 and 2,2′-bipyridine (bpy) [IrHCl(bpy)(PPh3)2]BPh 4 derivatives were also prepared using IrHCl2(PPh 3)3 as a precursor. The complexes were characterised spectroscopically (IR and NMR) and a geometry in solution was also established. Protonation with Br?nsted acid of pyrazole IrHCl2(Hpz) (PPh3)2 and imidazole IrHCl2(HIm)(PPh 3)2 complexes proceeded with the loss of the azole ligands and the formation of the unstable IrHCl2(PPh3) 2 derivative. Vinyl IrCl2{CHC(H)R1}(HRpz)P2 and IrCl2{CHC(H)R1}(HIm)P2 (R1 = Ph, p-tolyl, COOCH 3; P = PPh3, PiPr3) complexes were prepared by allowing hydride-pyrazole IrHCl2(HRpz)P2 and hydride-imidazole IrHCl2(HIm)P2 to react with an excess of terminal alkyne in 1,2-dichloroethane. The complexes were characterised spectroscopically and by the X-ray crystal structure determination of the IrCl2{CHC(H)Ph}(Hpz)(PPh3)2 derivative.

Iridium-assisted C≡C bond cleavage of 1-alkyne by water: Preparation of new alkyl derivatives

Alkyl complexes IrCl2(η1-CH2Ar)(CO) (PPh3)2 (1) [Ar = Ph (a), p-tolyl (b)] were prepared by allowing the hydride mer- or fac-IrHCl2(PPh3)3 to react with terminal alkynes ArC≡CH in the presence of water. The complexes were characterized spectroscopically (IR and 1H, 31P, 13C NMR) and by the X-ray crystal structure determination of 1b. The acyl complex IrCl2{C(O)CH2 C(CH3)3}(PPh3)2 (2) was also prepared by reacting mer-IrHCl2(PPh3)3 with tert-butylacetylene HC≡CC(CH3)3 in the presence of H2O. A reaction path for the hydration of terminal alkyne in the presence of the Ir(III) complex leading to the cleavage of the C≡C bond, with the formation of the complexes 1 or 2 is also proposed. Acetylide complexes IrHCl(C≡CAr) (PPh3)3 (3), IrHCl(C≡CAr) (AsPh3)3 (4) [Ar = Ph (a), p-tolyl (b)] and IrHCl(C≡CPh){PPh(OEt)2}(PPh3)2 (5) were prepared by reacting IrHCl2L3 (L = PPh3, AsPh3) or IrHCl2 {PPh(OEt)2}(PPh3)2 with lithium acetylide. Protonation reaction with Bronsted acids of the acetylide 3 was also studied and led to unstable vinyl derivatives. The stable vinyl [IrCl{η2-CH=C(H)COOMe}L2]BPh4 (6,7) [L = PPh3 (6), AsPh3 (7)] complexes, instead, were prepared by allowing IrHCl2L3 to react first with AgCF3SO3 and then with methyl propiolate.