17000-11-2

Basic information

• Product Name: IrCl(H)₂(CO)(PPh₃)₂
• CAS NO: 17000-11-2
• Molecular Weight: 782.281
• Mol File: 17000-11-2.mol

Chemical Properties

• CAS DataBase Reference: IrCl(H)₂(CO)(PPh₃)₂(CAS DataBase Reference)
• NIST Chemistry Reference: IrCl(H)₂(CO)(PPh₃)₂(17000-11-2)
• EPA Substance Registry System: IrCl(H)₂(CO)(PPh₃)₂(17000-11-2)

Safety Data

• Hazardous Substances Data: 17000-11-2(Hazardous Substances Data)

Upstream product

• 15318-31-7 bis(triphenylphosphine)iridium(I) carbonyl chloride 
• 33541-67-2 carbonylhydridotris(triphenylphosphine)iridium(I) 
• 1333-74-0 hydrogen 
• 16873-17-9 deuterium 
• 59246-46-7 bis(triphenylphosphine)carbonyliridium(I) chloride 
• 998-30-1 Triethoxysilane 
• 1079-66-9 chloro-diphenylphosphine 
• 1333-74-0 parahydrogen 
• 7789-20-0 water-d2 
• 7732-18-5 water 
• 21007-10-3 IrCl(H)(O₂CCF₃)(P(C₆H₅)3)2 
• 76-05-1 trifluoroacetic acid 
• 7646-69-7 sodium hydride 

Downstream Products

• 16971-53-2 mer,trans-IrH₃(CO)(PPh₃)2 
• 16971-53-2 fac-{IrH₃(PPh₃)2(CO)} 
• 38352-57-7 {IrCl(OOC(CH₃)3)2(CO)(P(C₆H₅)3)2} 
• 15318-31-7 bis(triphenylphosphine)iridium(I) carbonyl chloride 

Relevant articles and documents

Vibrational Couplings in Hydridocarbonyl Complexes: A 2D-IR Perspective

Hydridocarbonyl complexes, a class of industrially relevant catalysts, contain both the M-H and M-CO moieties. Here, using two-dimensional infrared spectroscopy, we examine the coupling of the typically weak M-H stretching mode and the intense M(CO) mode. By studying a series of Ir(I)- and Ir(III)-based hydridocarbonyl complexes, we show that the arrangement of the H and CO ligands in a trans configuration leads to strong vibrational coupling and mode delocalization. In contrast, a cis arrangement leads to no coupling, with the localized M-H mode having a much larger anharmonicity. These results highlight a promising strategy for enhancing the M-H vibration by intensity borrowing from the strong CO modes in a trans configuration, allowing for direct determination by infrared spectroscopy of both the oxidation (by frequency shifts) and the protonation state (via vibrational coupling) of the complex, in mechanistic studies of proton-coupled electron transfer reactions.

Photoinduced Cobalt(III)?Trifluoromethyl Bond Activation Enables Arene C?H Trifluoromethylation

Visible-light capture activates a thermodynamically inert CoIII?CF3 bond for direct C?H trifluoromethylation of arenes and heteroarenes. New trifluoromethylcobalt(III) complexes supported by a redox-active [OCO] pincer ligand were prepared. Coordinating solvents, such as MeCN, afford green, quasi-octahedral [(SOCO)CoIII(CF3)(MeCN)2] (2), but in non-coordinating solvents the complex is red, square pyramidal [(SOCO)CoIII(CF3)(MeCN)] (3). Both are thermally stable, and 2 is stable in light. But exposure of 3 to low-energy light results in facile homolysis of the CoIII?CF3 bond, releasing .CF3 radical, which is efficiently trapped by TEMPO. or (hetero)arenes. The homolytic aromatic substitution reactions do not require a sacrificial or substrate-derived oxidant because the CoII by-product of CoIII?CF3 homolysis produces H2. The photophysical properties of 2 and 3 provide a rationale for the disparate light stability.

Synthesis and reactivity of new bis(N-heterocyclic carbene) iridium(I) complexes

New complexes of the type trans-[IrCl(η2-COE)(NHC) 2] (COE = cis-cyclooctene; NHC = N-heterocyclic carbene) have been prepared in one step from the reaction of ca. 4 equiv of NHC or [AgCl(NHC)] with [IrCl(η2-COE)2/su

Comparative reactivity of triorganosilanes, HSi(OEt)3 and HSiEt3, with IrCl(CO)(PPh3)2. Formation of IrCl(H)2(CO)(PPh3)2 or Ir(H)2(SiEt3)(CO)(PPh3

Reaction of HSi(OEt)3 with IrCl(CO)(PPh3)2 (5:1 molar ratio) at room temperature for 1 h gives IrCl(H){Si(OEt)3}(CO)(PPh3)2 (1), which is observed by the 1H and 31P{s

Transition state characterization for the reversible binding of dihydrogen to bis(2,2′-bipyridine)rhodium(I) from temperature- and pressure-dependent experimental and theoretical studies

Thermodynamic and kinetic parameters for the oxidative addition of H 2 to [RhI(bpy)2]+ (bpy = 2,2′-bipyridine) to form [RhIII(H)2(bpy) 2]+ were determined from either the UV-vis spectrum of equilibrium mixtures of [RhI(bpy)2]+ and [RhIII(H)2(bpy)2]+ or from the observed rates of dihydride formation following visible-light irradiation of solutions containing [RhIII(H)2(bpy)2] + as a function of H2 concentration, temperature, and pressure in acetone and methanol. The activation enthalpy and entropy in methanol are 10.0 kcal mol-1 and -18 cal mol-1 K-1, respectively. The reaction enthalpy and entropy are -10.3 kcal mol-1 and -19 cal mol-1 K-1, respectively. Similar values were obtained in acetone. Surprisingly, the volumes of activation for dihydride formation (-15 and -16 cm3 mol-1 in methanol and acetone, respectively) are very close to the overall reaction volumes (-15 cm3 mol-1 in both solvents). Thus, the volumes of activation for the reverse reaction, elimination of dihydrogen from the dihydrido complex, are approximately zero. B3LYP hybrid DFT calculations of the transition-state complex in methanol and similar MP2 calculations in the gas phase suggest that the dihydrogen has a short H-H bond (0.823 and 0.810 A, respectively) and forms only a weak Rh-H bond (1.866 and 1.915 A, respectively). Equal partial molar volumes of the dihydrogenrhodium(I) transition state and dihydridorhodium(III) can account for the experimental volume profile found for the overall process.

Bridging the gap between homogeneous and heterogeneous catalysis: Ortho/para H2 conversion, hydrogen isotope scrambling, and hydrogenation of olefins by Ir(CO)Cl(PPh3)2

Some transition metal complexes are known to catalyze ortho/para hydrogen conversion, hydrogen isotope scrambling, and hydrogenation reactions in liquid solution. Using the example of Vaska's complex, we present here evidence by NMR that the solvent is no

Activation of H2 by halocarbonyl bis-phosphine and bis-arsine iridium(I) complexes. The use of parahydrogen induced polarisation to detect species present at low concentration and investigate their reactivity

The iridium phosphine complexes Ir(CO)Cl(L)2 [L = PPh3, PMe3, AsPh3 and PPh2Cl, and L2 = (PPh2Cl)(PPh3)] add H2 to form the corresponding dihydrides IrH2(CO)Cl(L)2. These products are detected at enhanced levels of sensitivity through the 1H NMR signatures of their hydride resonances via para-hydrogen (p-H2) based spin state synthesis. Products corresponding to addition across both the Cl-Ir-CO and L-Ir-L axes are detected. For L = PPh3, there is a 100 fold preference for the former pathway at 295 K, while for L = AsPh3 the second product is favoured by a factor of 2.85. At elevated temperatures a third product corresponding to addition over the Cl-Ir-L axis is detected for L = AsPh3 and PPh2Cl. Under these conditions, the CO and HCl transfer products Ir(H)3(CO)2(AsPh3), and IrH(CO)Cl2(AsPh3)2 are also formed in a thermal reaction. When IrH2(CO)Cl(L)2 is warmed or photolysed with H2 and CO, the corresponding products are produced for L = PPh3 and PMe3. However after photolysis with H2 alone Ir(H)3(CO)(L)2 is the favoured product. Additional products detected during the photochemical studies include Ir(H)2(PPh)3(PPh2C5H4 CO), an unusual orthometallation product containing an η2-acyl ligand, and the binuclear products H(Cl)Ir(PMe3)2(μ-H)(μ-Cl)Ir(PMe3)(CO) and (H)2Ir(PMe3)2(μ-Cl)2Ir(PMe) 3(CO).

New products in an old reaction: Isomeric products from H2 addition to Vaska's complex and its analogues

para-Hydrogen enhanced NMR signals aid detection of minor isomers of complexes IrH2(L)2(CO)Cl (L = PPh3, PMe3, PPh2Cl and AsPh3) containing magnetically inequivalent hydride ligands that ar

Structure and Dynamics in Metal Phosphine Complexes Using Advanced NMR Studies with Para-hydrogen Induced Polarisation

The iridium and rhodium phosphine complexes IrCl(CO)(PPh3)2 1 (Vaska's complex), Rh(PMe3)4Cl 2, and Rh(PMe3)3Cl 3, add H2 to form the corresponding dihydrides. Exchange with para-hydrogen (p-H2) provides a means of observing 1H NMR signals due to the metal bound hydrides at significantly enhanced levels of sensitivity. We show that monitoring these metal hydride complexes can be achieved by a range of 2D NMR methods, based on standard experiments, which have been modified to achieve optimum signal. This assignment of heteronuclei, including low sensitivity nuclei such as 103Rh, determination of heteronuclear coupling constants and measurement of their relative signs, is described for these systems using p-H2 derived starting magnetisation. In the case of Vaska's complex the dihydride addition product contains a trans labilised carbonyl ligand, and substitutiion with appropriate phosphines brings about the formation of metal phosphine complexes with new ligand spheres. Appropriately modified NOESY experiments are demonstrated to rapidly probe structural arrangements, and monitor dihydride exchange. For Ir(H)2Cl(PPh3)3 dihydride exchange is shown to proceed mainly via Ir(H)2Cl(PPh3)2, which is shown to contain inequivalent hydrides. The reactivity of the arsine complex IrCl(AsPh3)3 9 towards H2 is examined, and the NOESY approach used to make structural assignments in the reaction product.

Solvent effect for oxidative addition of hydrogen in solvents from toluene to water: Reaction of H2 with trans-[Ir(CO)Cl{PPh2(C6H4SO 3K-m)}2]

A significant enhancement in the rate of oxidative addition of H2 to square-planar iridium(II) complexes in water is observed; kinetic studies of the addition of H2 to trans-[Ir(CO)Cl(PPh3)2] in toluene and of H2 to trans-[Ir-(CO)Cl{PPh2(C6H4SO 3K-m)}2] in water show a factor of 45 increase in rate constant in water; this solvent effect is shown to be general for the solvents toluene, chlorobenzene, N,N-dimethylformamide, dimethyl sulfoxide and water, and has important ramifications for catalysis in water.