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Activation of Aliphatic Ethers by TpMe2Ir Compounds: Multiple C−H Bond Activation and C−C Bond Formation

AuthorsÁlvarez, Eleuterio ; Paneque, Margarita ; Guerreiro de Brito Petronilho, Ana Rita ; López Poveda, Manuel ; López Santos, Laura; Carmona, Ernesto ; Mereiter, Kurt
KeywordsAliphatic ethers
C-H activation
C-C formation
Hydride carbenes
Issue Date3-Feb-2007
PublisherAmerican Chemical Society
CitationOrganometallics 26(5): 1231-1240 (2007)
AbstractBenzene solutions of the unsaturated fragment TpMe2Ir(C6H5)2 (1), generated in situ from either TpMe2Ir(C2H4)2 or TpMe2Ir(C6H5)2(N2), react with methyl ethers MeOBut, MeOBun, and MeOCH2CH2OMe to give the organometallic hydride carbene products TpMe2(H)2( C(H)OR) 4 (R = But, 4a; Bun, 4b; CH2CH2OMe, 4c) along with benzylic ethers C6H5CH2OR 5. The overall reaction is very complex and involves the participation of two molecules of the ether, MeOR, and one of benzene per molecule of the iridium precursor. The latter induces multiple C−H bond cleavage along with the formation of a new C−C bond. Hydride carbenes of composition TpMe2Ir(H)(C6H5)(C (H)OR) (2) are early intermediates of this reaction. They can be shown to undergo a reversible 1,2-H shift between the metal atom and the carbene carbon atom, until eventually β-H elimination from the Ir−C6H5 unit allows the C−C coupling through a nonisolable benzyne intermediate. Me−OR bond cleavage, although somewhat more energetically demanding than C−H activation, can also occur and has been demonstrated in the reaction of 1 with Me−OBun, which permits the isolation of the hydride n-propyl carbonyl complex TpMe2Ir(H)(CH2CH2CH3)(CO), 10b.
Description10 páginas, 4 figuras, 1 tabla, 8 esquemas.
Publisher version (URL)http://dx.doi.org/10.1021/om0609822
Appears in Collections:(IIQ) Artículos
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