1194784-58-1

Basic information

• Product Name: [(κ3-C6H3-2,6-[CH2P(t-Bu)2]2)Ir(CH3)(3,5-bis(trifluoromethyl)phenoxide)]
• Synonyms: [(κ3-C6H3-2,6-[CH2P(t-Bu)2]2)Ir(CH3)(3,5-bis(trifluoromethyl)phenoxide)]
• CAS NO: 1194784-58-1
• Molecular Weight: 829.909
• Mol File: 1194784-58-1.mol

Chemical Properties

• CAS DataBase Reference: [(κ3-C6H3-2,6-[CH2P(t-Bu)2]2)Ir(CH3)(3,5-bis(trifluoromethyl)phenoxide)](CAS DataBase Reference)
• NIST Chemistry Reference: [(κ3-C6H3-2,6-[CH2P(t-Bu)2]2)Ir(CH3)(3,5-bis(trifluoromethyl)phenoxide)](1194784-58-1)
• EPA Substance Registry System: [(κ3-C6H3-2,6-[CH2P(t-Bu)2]2)Ir(CH3)(3,5-bis(trifluoromethyl)phenoxide)](1194784-58-1)

Safety Data

• Hazardous Substances Data: 1194784-58-1(Hazardous Substances Data)

Upstream product

• 312960-77-3 [(κ3-C6H3-2,6-[CH2P(t-Bu)2]2)Ir(tert-butylvinyl)(H)] 
• 349-60-0 1-methoxy-3,5-bis(trifluoromethyl)benzene 
• 1427804-33-8 C₃₃H₄₉F₆IrOP₂ 

Relevant articles and documents

Cleavage of sp3 C-O bonds via oxidative addition of C-H bonds

(Chemical Equation Presented) (PCP)Ir (PCP = K3-C 6H3-2,6-[CH2P(t-Bu) 2]2) is found to undergo oxidative addition of the methyl-oxygen bond of electron-poor methyl aryl ethers, i

Cleavage of ether, ester, and tosylate C(sp3)-O bonds by an iridium complex, initiated by oxidative addition of C-H bonds. Experimental and computational studies

A pincer-ligated iridium complex, (PCP)Ir (PCP = κ3-C 6H3-2,6-[CH2P(t-Bu)2]2), is found to undergo oxidative addition of C(sp3)-O bonds of methyl esters (CH3-O2CR′), methyl tosylate (CH 3-OTs), and certain electron-poor methyl aryl ethers (CH 3-OAr). DFT calculations and mechanistic studies indicate that the reactions proceed via oxidative addition of C-H bonds followed by oxygenate migration, rather than by direct C-O addition. Thus, methyl aryl ethers react via addition of the methoxy C-H bond, followed by α-aryloxide migration to give cis-(PCP)Ir(H)(CH2)(OAr), followed by iridium-to-methylidene hydride migration to give (PCP)Ir(CH3)(OAr). Methyl acetate undergoes C-H bond addition at the carbomethoxy group to give (PCP)Ir(H) [κ2-CH2OC(O)Me] which then affords (PCP-CH 2)Ir(H)(κ2-O2CMe) (6-Me) in which the methoxy C-O bond has been cleaved, and the methylene derived from the methoxy group has migrated into the PCP Cipso-Ir bond. Thermolysis of 6-Me ultimately gives (PCP)Ir(CH3)(κ2-O2CR), the net product of methoxy group C-O oxidative addition. Reaction of (PCP)Ir with species of the type ROAr, RO2CMe or ROTs, where R possesses β-C-H bonds (e.g., R = ethyl or isopropyl), results in formation of (PCP)Ir(H)(OAr), (PCP)Ir(H)(O2CMe), or (PCP)Ir(H)(OTs), respectively, along with the corresponding olefin or (PCP)Ir(olefin) complex. Like the C-O bond oxidative additions, these reactions also proceed via initial activation of a C-H bond; in this case, C-H addition at the β-position is followed by β-migration of the aryloxide, carboxylate, or tosylate group. Calculations indicate that the β-migration of the carboxylate group proceeds via an unusual six-membered cyclic transition state in which the alkoxy C-O bond is cleaved with no direct participation by the iridium center.