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

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

Uses

Chloro(1,5-cyclooctadiene)iridium(I) dimer is used as a precursor for the synthesis of other iridium complexes that are employed in homogeneous catalysis. The applications of these complexes are diverse and include:
1. Carbonylation: The iridium complexes derived from this dimer are used to catalyze the carbonylation of various substrates, which is a crucial reaction in the production of chemicals such as pharmaceuticals and agrochemicals.
2. Hydrosilylation: These complexes are also utilized in hydrosilylation reactions, which involve the addition of a silicon-hydrogen bond to an unsaturated compound, such as an alkene or alkyne. This reaction is essential in the synthesis of organosilicon compounds.
3. Hydroformylation: The iridium complexes are used as catalysts in hydroformylation reactions, where an aldehyde is produced by the addition of a hydrogen and carbon monoxide molecule to an alkene.
4. Asymmetric Allylic Substitutions: The dimer's derived complexes are employed in asymmetric allylic substitutions, which are vital in the synthesis of enantiomerically pure compounds, essential in the pharmaceutical and agrochemical industries.
5. Metathesis: The iridium complexes are used as catalysts in olefin metathesis reactions, which involve the redistribution of carbon-carbon double bonds in olefins. This reaction is crucial in the synthesis of complex organic molecules and polymers.
6. Chiral Catalysis: The derived iridium complexes are used in chiral catalysis, where they facilitate enantioselective reactions, leading to the formation of optically active compounds with a single enantiomer.
7. Preparation of Crabtree's Catalyst: Chloro(1,5-cyclooctadiene)iridium(I) dimer is involved in the preparation of Crabtree's catalyst, which is widely used for hydrogenation and hydrogen-transfer reactions. These reactions are essential in the synthesis of various organic compounds, including pharmaceuticals and fine chemicals.

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

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 
• 1552-12-1 1,5-cis,cis-cyclooctadiene 
• 92561-82-5 iridium tetrachloride monohydrate 
• 7782-50-5 chlorine 

Downstream Products

• 340270-34-0 IrCl(1,5-cyclooctadiene)(1,3-bis(diphenylphosphino)propane) 
• 953087-76-8 [Ir(I)(salicylidenebenzyliminato)(1,5-cyclooctadiene)] 
• 12154-84-6 η4-1,5-cyclooctadiene-μ-2,4-pentanedionato-iridium(I) 
• 32761-45-8 [Ir(I)(salicylidenephenyliminato)(1,5-cyclooctadiene)] 
• 501909-58-6 [Ir(III)(η(3)-CH2CHCHPh)(Cl)2(η(4)-1,5-COD)] 
• 64536-83-0 [IrCl(cod)(PCy₃)] 
• 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.

Polymerization of phenylacetylene catalyzed by organoiridium compounds

The compounds [Ir(cod)X]2 (cod = 1,5-cyclooctadiene; X = Cl, OMe) catalyze the polymerization of phenylacetylene, with negligible formation of oligomeric products. At variance, the monoolefin analogue [Ir(cot)2Cl]2 (cot = cyclooctene) only promotes alkyne cyclotrimerization. The polymerization reaction proceeds in various solvents such as tetrahydrofuran (THF), chloroform and benzene, but it is most favored when using NEt3 as reaction medium. The role of the diene in the catalytic reaction is investigated, also in relation to a deactivation process of the catalyst with time. Spectroscopic studies of the catalytic reaction indicate the formation of monomeric iridium-solvent adducts, which are likely to be the initiators of the polymerization reaction. A possible reaction mechanism is proposed, according to the data reported in the literature and the results of the present investigation.

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.

Synthesis and characterisation of a novel mixed donor P,O,P' nixantphos ligand and its metal complex

The complex [(NixC8OH)Ir(cod)Cl] 4 has been synthesized and structurally characterized by NMR, IR and single crystal X-ray diffraction. The synthesis and characterisation of the novel ligand NixC8OH is also presented. The coordination around Ir is trigonal bipyramidal with both P groups of the NixC8OH ligand bound in a bis-equatorial mode. The bis-chelating cod (C8H12) ligand occupies the remaining equatorial position and an axial position. This mode of bonding has resulted in a large bite angle (P1-Ir-P2) of 102.92(12)° for the title complex 4. The IR and NMR data further support the elucidated structure. Thermal analyses of 4 indicate that it is thermally stable up to a decomposition temperature of >400 °C.

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.

Vapor pressure of some volatile iridium(I) compounds with carbonyl, acetylacetonate and cyclopentadienyl ligands

Volatile compounds of iridium(I): (acetylacetonato)(1,5-cyclooctadiene) iridium(I) Ir(acac)(cod), (methylcyclopentadienyl) (1,5-cyclooctadiene) iridium(I) Ir(Cp')(cod), (pentamethylcyclopentadienyl)(dicarbonyl) iridium(I) Ir(Cp*)(CO)2 and (acet

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).

Fluorine-free blue-green emitters for light-emitting electrochemical cells

There is presently a lack of efficient and stable blue emitters for light-emitting electrochemical cells (LEECs), which limits the development of white light emitting systems for lighting. Cyclometalated iridium complexes as blue emitters tend to show low photoluminescence efficiency due to significant ligand-centred character of the radiative transition. The most common strategy to blue-shift the emission is to use fluorine substituents on the cyclometalating ligand, such as 2,4-difluorophenylpyridine, dFppy, which has been shown to decrease the stability of the emitter in operating devices. Herein we report a series of four new charged cyclometalated iridium complexes using methoxy- and methyl-substituted 2,3′-bipyridine as the main ligands. The combination of donor groups and the use of a cyclometalated pyridine has been recently reported for neutral complexes and found electronically equivalent to dFppy. We describe the photophysical and electrochemical properties of the complexes in solution and use DFT and TDDFT calculations to gain insights into their properties. The complexes exhibit bluish-green emission with onsets around 450 nm, which correspond to the maximum emission at 77 K. Furthermore, photoluminescence quantum yields in solution are all above 40%, with the brightest in the series at 66%. Finally, LEECs were prepared using these complexes as the emissive material to evaluate the performance of this particular design. Compared to previously reported devices with fluorine-containing emitters, the emitted colours are slightly red-shifted due to methyl substituents on the coordinating pyridine of the main ligand and overall device performances, unfortunately including the stability of devices, are similar to those previously reported. Interestingly within the series of complexes there appears to be a positive effect of the methoxy-substituents on the stability of the devices. The poor stability is therefore attributed to the combination of cyclometalated pyridine and methoxy groups. the Partner Organisations 2014.

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.

Preparation method of (1,5-cyclooctadiene) methoxy iridium (I) dimer

The invention discloses a preparation method of a (1,5-cyclooctadiene)methoxy iridium (I) dimer, which comprises the following steps: (1) mixing iridium powder and sodium chloride, purging the mixturewith N2, performing chlorination, dissolving the obtained solid powder in a hydrochloric acid solution, and stirring the solution to obtain a sodium chloroiridate water solution; (2) enabling the sodium chloroiridate aqueous solution to pass through acidic cation exchange resin to obtain a chloroiridic acid aqueous solution; (3) under the protection of N2, adding 1,5-cyclooctadiene into ethanol,increasing the temperature, dropwise adding a chloroiridic acid aqueous solution into the ethanol, stirring the mixture for reaction after dropwise adding is finished, cooling a reaction product to room temperature, and performing crystallization and filtration to obtain a (1,5-cyclooctadiene) iridium chloride (I) dimer; and (4) adding potassium hydroxide into methanol, heating and stirring the mixture, adding the (1,5-cyclooctadiene) iridium chloride (I) dimer, performing a reaction for 3-6 hours, cooling and filtering the reaction product, washing the reaction product with water, and carrying out vacuum drying to obtain the product. The method provided by the invention has the advantages of high product yield and high purity.