12112-67-3

Basic information

• Product Name: Chloro(1,5-cyclooctadiene)iridium(I) dimer
• Synonyms: BIS(1,5-CYCLOOCTADIENE)DIIRIDIUM(I) DICHLORIDE;DI-MU-CHLOROBIS[(ETA-CYCLOOCTA-1,5-DIENE)IRIDIUM (I)];DI-MU-CHLORO-BIS[(1,2,5,6-ETA)-1,5-CYCLOOCTADIENE]DIIRIDIUM;CHLORO(1,5-CYCLOOCTADIENE)IRIDATE (I) DIMER;CHLORO(1,5-CYCLOOCTADIENE)IRIDIUM(I) DIMER;IRIDIUM(I) CHLORIDE 1,5-CYCLOOCTADIENE COMPLEX DIMER;IRIDIUM I CYCLOOCTADIENE CHLORIDE;IRIDIUM CHLORO-1,5-CYCLOOCTADIENE
• CAS NO: 12112-67-3
• Molecular Formula: C₁₆H₂₄Cl₂Ir₂
• Molecular Weight: 671.7
• EINECS: 235-170-1
• Product Categories: Ir (Iridium) Compounds;Catalysts for Organic Synthesis;Classes of Metal Compounds;Homogeneous Catalysts;Metal Complexes;Synthetic Organic Chemistry;Transition Metal Compounds;organometallic complexes;Ir
• Mol File: 12112-67-3.mol
• Article Data: 18

Chemical Properties

• Melting Point: 205 °C (dec.)(lit.)
• Boiling Point: 153.5ºC at 760 mmHg
• Flash Point: 31.7ºC
• Appearance: red to orange/Powder
• Vapor Pressure: 4.25mmHg at 25°C
• Storage Temp.: 2-8°C
• Water Solubility: insoluble
• CAS DataBase Reference: Chloro(1,5-cyclooctadiene)iridium(I) dimer(CAS DataBase Reference)
• NIST Chemistry Reference: Chloro(1,5-cyclooctadiene)iridium(I) dimer(12112-67-3)
• EPA Substance Registry System: Chloro(1,5-cyclooctadiene)iridium(I) dimer(12112-67-3)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-37/39
• WGK Germany: 3
• F: 10
• TSCA: No
• Hazardous Substances Data: 12112-67-3(Hazardous Substances Data)

Usage

Reactions

1. Precursor to catalysts for the asymmetric hydrogenation of tri- and tetrasubstituted olefins. 2. Precursor to catalyst for enantioselective reduction of imines. 3. Precursor to catalyst for allylic alkylation. 4. Precursor to catalyst for allylic amination and etherification. 5. Precursor to catalyst for the reaction of aroyl chlorides with internal alkynes to produce substituted naphthalenes and anthracenes. 6. Ir-catalyzed addition of acid chlorides to terminal alkynes. 7. Intramolecular hydroamination of unactivated alkenes with secondary alkyl- and arylamines. 8. Enantioselective [2+2] cycloaddition. 9. Silyl-directed, Ir-catalyzed ortho-borylation of arenes. 10. Ir-catalyzed cross-coupling of styrene derivatives with allylic carbonates. 11. Transfer hydrogenative C-C coupling

Chemical Properties

red-orange solid

Uses

Chloro(1,5-cyclooctadiene)iridium(I) dimer is widely used as a precursor to other iridium complexes, which finds application in homogeneous catalysis like carbonylation, hydrosilylation, hydrofomylation, asymmetric allylic substitutions, metathesis and chiral catalysis reactions. It is involved in the preparation of Crabtree's catalyst, which is used for hydrogenation and hydrogen-transfer reactions.

InChI:InChI=1/2C8H12.2ClH.2Ir/c2*1-2-4-6-8-7-5-3-1;;;;/h2*1-2,7-8H,3-6H2;2*1H;;/p-2/b2*2-1-,8-7-;;;;

Upstream product

• 5259-72-3 cyclo-octa-1,5-diene 
• 7782-50-5 chlorine 
• 92561-82-5 iridium tetrachloride monohydrate 
• 1552-12-1 1,5-cis,cis-cyclooctadiene 

Downstream Products

• 12154-84-6 η4-1,5-cyclooctadiene-μ-2,4-pentanedionato-iridium(I) 
• 32761-45-8 [Ir(I)(salicylidenephenyliminato)(1,5-cyclooctadiene)] 
• 672297-76-6 [IrCl(κ(1)-NH=CPh2)(η(4)-C8H12)] 
• 521916-35-8 [IrCl(CO)(diphenyl(2,6-dimethylphenyl)phosphine)2] 
• 659723-44-1 [Ir(COD)((5-diphenylphosphanylpyrazol-1-yl)(diphenylphosphanyl)(pyrazol-1-yl)methane)]BF₄ 
• 675582-88-4 [Ir(1,5-cyclooctadiene)(1-[2-(diphenylphosphino)ethyl]pyrazole)](BPh₄) 
• 615263-71-3 (η4-1,5-cyclooctadiene)iridium(I)(Ph2PCH2CMe2NH) 
• 586353-32-4 (ethene)[N,N,N-tris(2-pyridylmethyl-κN)amine-κN]iridium(I) tetraphenylborate 
• 586353-02-8 bis(ethene)[N-(2-pyridylmethyl)-N,N-bis(2-pyridylmethyl-κN)amine-κN]iridium(I) tetraphenylborate 
• 623948-46-9 (bis(N-methylimidazol-2-yl)methane)dicarbonyliridium(I) tetraphenylborate 
• 550373-50-7 [bis(3,5-dimethyl-1-pyrazolyl)methane]dicarbonyliridium(I) tetraphenylborate 
• 550373-45-0 [bis(1-pyrazolyl)methane](1,5-cyclooctadiene)iridium(I) tetraphenylborate 
• 550373-47-2 [bis(3,5-dimethyl-1-pyrazolyl)methane](1,5-cyclooctadiene)iridium(I) tetraphenylborate 
• 521916-32-5 [IrHCl(CO)(η2-Ph2PCH2CO2)(η1-diphenylphosphinoacetic acid)] 

Relevant articles and documents

Nanostructured IrOx Coatings for Efficient Oxygen Evolution Reactions in PV-EC Setup

New heteroleptic iridium compounds exhibiting high volatility and defined thermal decomposition behavior were developed and tested in plasma-enhanced chemical vapor deposition (PECVD). The iridium precursor [(COD)Ir(TFB-TFEA)] (COD = 1,5-cyclooctadiene; TFB-TFEA = N-(4,4,4-Trifluorobut-1-en-3-on)-6,6,6-trifluoroethylamin) unifies both reactivity and sufficient stability through its heteroleptic constitution to offer a step-by-step elimination of ligands to provide high compositional purity in CVD deposits. The substitution of neutral COD ligands against CO groups further increased the volatility of the precursor. PECVD experiments with unambiguously characterized Ir compounds (single crystal X-ray diffraction analysis) demonstrated their suitability for an atom-efficient (high molecule-to-precursor yield) gas phase deposition of amorphous iridium oxide (IrOx) phases. Thin films of IrOx were well suited as electrocatalyst in oxygen evolution reaction so that an efficient coupled system in combination with solar cells is viable to perform water-splitting reaction without external bias.

Subvalent Iridium Precursors for Atom-Efficient Chemical Vapor Deposition of Ir and IrO2 Thin Films

A new heteroleptic Ir(I) compound exhibiting high volatility and defined thermal decomposition under CVD conditions is reported. The new iridium precursor [(COD)Ir(ThTFP)] (COD = cyclooctadiene, ThTFP = (Z)-3,3,3-trifluoro-1-(thiazol-2-yl)prop-1-en-2-olate) unifies both reactivity and sufficient stability through its heteroleptic constitution to provide a precise control over compositional purity in CVD deposits. The solution integrity of the monomeric Ir(I) complex was investigated by 1D and 2D NMR spectroscopy and EI mass spectrometry, whereas the molecular structure was confirmed by single-crystal diffraction. CVD experiments demonstrated the suitability of the iridium compound for an atom-efficient (high molecule-to-precursor yield) gas-phase deposition of nanocrystalline iridium films that could be converted into crystalline iridium dioxide upon heat treatment to demonstrate their electrocatalytic potential in the oxygen evolution reaction.

A kinetic investigation of the oxidative addition reactions of the dimeric Bu4N[Ir2(μ-Dcbp)(cod)2] complex with iodomethane

The kinetic results of the oxidative addition of iodomethane to Bu4N[Ir2(μ-Dcbp)(cod)2] (Dcbp = 3,5-dicarboxylatepyrazolate anion) show that oxidative addition can occur via a direct equilibrium pathway (K1 = 88(22) acetone, 51(3) 1,2-dichloroethane, 55(4) dichloromethane, 52(12) acetonitrile and 43(5) M-1 chloroform) or a solvent-assisted pathway (k2, k3). Oxidative addition occurs mainly along the direct pathway, which is a factor 10-40 faster than the solvent-assisted pathway. The observed solvent effect cannot be attributed to the donosity or polarity of the solvents. The fairly negative ΔS≠ value (-110(7) J K-1 mol-1) and the positive ΔH≠ value (+47(2) kJ mol-1) for the oxidative addition step are indicative of an associative process.

Luminescent iridium(III) complexes supported by a tetradentate trianionic ligand scaffold with mixed O, N, and C donor atoms: Synthesis, structures, photophysical properties, and material applications

A panel of tetradentate H3-O^N^C^O ligands has been synthesized and employed as a trianionic scaffold for preparing [IrIII(O^N^C^O)(L)2], with L = a wide variety of neutral ligands, and also [IrIII(O^N^C^O)(C≡NAr)(NH2Ar)], [IrIII(O^N^C^O)(C≡NAr)(X)] (Ar = 2,6-Me2C6H3; X = 1-methylimidazole, PPh3, pyridine), and [IrIII(O^N^C^O)- (NHC)]2 (NHC = N-heterocyclic carbene). X-ray crystal structure analysis and photophysical studies (including variable-temperature emission lifetime measurements and nanosecond time-resolved emission and absorption spectroscopy) were performed. [Ir(O^N^C^O)(L)2] display a moderately strong phosphorescence at room temperature (emission quantum yields up to 18% in solution, 51% in PMMA film), with the luminescent properties being strongly affected by axial L ligands. The use of [Ir(O^N^C^O)(NHC)2] as a phosphorescent emitter in a solution-processed organic light-emitting diode device generated a red electrophosphorescence with an EQE of 10.5% and CIE chromaticity coordinates of (0.64, 0.36).

Preparation method of iridium catalyst

The invention discloses a preparation method of an iridium catalyst [IrCl(C8H12)]2. The preparation method comprises following steps: a compound containing iridium and chlorine is dissolved in water in an oxygen-free environment, and an iridium solution is prepared; cyclooctadiene is added to the iridium solution, a reducing agent is slowly dropwise added for a reduction reaction, and the reducingagent is dropwise added until no precipitates are produced; the solution is filtered, evaporative crystallization is performed after solids are washed with water, and [IrCl(C8H12)]2 is obtained. According to the method, the reaction time is short, and the product is high in purity and yield.

Iridium(I)-Catalyzed C?H Borylation in Air by Using Mechanochemistry

Mechanochemistry has been applied for the first time to an iridium(I)-catalyzed C?H borylation reaction. By using either none or just a catalytic amount of a liquid, the mechanochemical C?H borylation of a series of heteroaromatic compounds proceeded in air to afford the corresponding arylboronates in good-to-excellent yields. A one-pot mechanochemical C?H borylation/Suzuki–Miyaura cross-coupling sequence for the direct synthesis of 2-aryl indole derivatives is also described. The present study constitutes an important milestone towards the development of industrially attractive solvent-free C?H bond functionalization processes in air.