102525-11-1

Basic information

• Product Name: 1,5-CYCLOOCTADIENE(H5-INDENYL)IRIDIUM (I)
• Synonyms: 1,5-CYCLOOCTADIENE(H5-INDENYL)IRIDIUM (I);(1,5-CYCLOOCTADIENE)(ETA5-INDENYL)IRID&;1,5-Cyclooctadiene(h5-indenyl)iridium(I),99%;(1,5-Cyclooctadiene)-η:5-indenyl)iridium(I);1,5-Cyclooctadiene(η5-indenyl) iridium(I), 99%;1,5-Cyclooctadiene(eta5-indenyl)iridium(I);(1Z,5Z)-cycloocta-1,5-diene:indene:iridium;5-indenyl)iridium(I), 99%
• CAS NO: 102525-11-1
• Molecular Formula: C₁₇H₁₉Ir
• Molecular Weight: 415.55
• Product Categories: Catalysis and Inorganic Chemistry;Chemical Synthesis;Iridium;organometallic complex;Ir
• Mol File: 102525-11-1.mol

Chemical Properties

• Melting Point: 126-131 °C
• Appearance: yellow/crystal
• CAS DataBase Reference: 1,5-CYCLOOCTADIENE(H5-INDENYL)IRIDIUM (I)(CAS DataBase Reference)
• NIST Chemistry Reference: 1,5-CYCLOOCTADIENE(H5-INDENYL)IRIDIUM (I)(102525-11-1)
• EPA Substance Registry System: 1,5-CYCLOOCTADIENE(H5-INDENYL)IRIDIUM (I)(102525-11-1)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36/37/39
• WGK Germany: 3
• TSCA: No
• Hazardous Substances Data: 102525-11-1(Hazardous Substances Data)

Usage

Uses

Catalyst for C-H activation/borylation

InChI:InChI=1/C9H7.C8H12.Ir/c1-2-5-9-7-3-6-8(9)4-1;1-2-4-6-8-7-5-3-1;/h1-7H;1-2,7-8H,3-6H2;/b;2-1-,8-7-;

Upstream product

• 75751-34-7 (C₉H₈)Ir(C₈H₁₂)⁽¹⁺⁾*BF₄^(1-)={(C₉H₈)Ir(C₈H₁₂)}BF₄ 
• 20734-58-1 N,N,N',N'-tetramethyl-1,8-diaminonaphthalene 
• 95-13-6 1-indene 
• 20669-47-0 indenyllithium 

Downstream Products

• 118494-48-7 [tris-(trimethylphosphine)(cyclooctadiene)iridium(I)]chloride 
• 18053-75-3 3-Trimethylsilylinden 

Relevant articles and documents

Kinetics and mechanism of indene C-H bond activation by [(COD)Ir(μ2-OH)]2

The hydroxy-bridged dimer [(COD)Ir(μ2-OH)]2 (COD = 1,5-cyclooctadiene) cleanly cleaves C-H bonds in indene and cyclopentadiene to produce (COD)Ir(η3-indenyl) and (COD)Ir(η5-C 5H5), respectively. The kinetics of the formation of (COD)Ir(η3-indenyl) are consistent with a mechanism that involves coordination of indene to [(COD)Ir(μ2-OH)]2 followed by rate-determining C-H activation from the iridium dimer-indene unit. Transition-state analysis of the Ir and Rh hydroxy dimers indicates that the C-H activation proceeds through a direct deprotonation of indene by the M-OH unit rather than a stepwise oxidative addition/reductive elimination mechanism. The crystal structure of [(COD)Ir]5(μ4-O)(μ3- O)(μ2-OH), a dehydration product of [(COD)Ir(μ2-OH)] 2, is presented.

Observation of intermediates in the protonation of (η5-C9H7)Ir(η4-C 8H12) with CF3CO2H

Protonation of (η5-C9H7)Ir(η4-C 8H12) (1) in CDCl3 at -50°C with 1 equiv of trifluoroacetic acid resulted initially in the formation of free indene and a species assigned as the dinuclear iridium cyclooctadiene complex (Ir(η4-C8H12)(μ-O2CCF 3))2 (2); the mixture slowly reacted to give [(η6-C9H8)Ir(η4-C 8H12)]+ (3). The metal protonated form of 1, [(η5-C9H7)Ir(η4-C 8H12)H]+ (1H+), was observed only at low temperature in the presence of excess acid. Proton abstraction from 3·[BF4] with Proton Sponge in dichloromethane gave 1.

Synthesis and reaction chemistry of (η5-indenyl)(cyclooctadiene)iridium: Migration of indenyl from iridium to cyclooctadiene

(η5-Indenyl)(cyclooctadiene)iridium was synthesized in high yield from chloro(cyclooctadiene)iridium dimer and lithium indenide. The reaction chemistry of the above compound was investigated with respect to the displacement of the cyclooctadiene with various nucleophiles. Thus, (η5-indenyl)dicarbonyliridium could be synthesized in high yield by treating the cyclooctadiene complex with carbon monoxide at atmospheric pressure. However, the addition of trimethylphosphine, PMe3, to the cyclooctadiene complex resulted not in the displacement of cyclooctadiene but in the migration of indene from iridium to cyclooctadiene forming (2-indenylcyclooct-5-en-1-yl)tris(trimethylphosphine)iridium, I, quantitatively. A single-crystal X-ray structural determination of I was carried out and confirmed the migration of indene to the cyclooctadiene. I crystallizes in the orthorhombic space group P212121 with a = 10.019 (1) A?, b = 18.836 (3) A?, c = 29.602 (4) A?, V = 5586 (2) A?3, and Z = 8. The syntheses of a related series of (trimethylsilyl-substituted indenyl)iridium complexes are also reported along with some suggestions for the mechanism of the iridium to cyclooctadiene indenyl migration.