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• W2152520153 endingPage "1809" @default.
• W2152520153 startingPage "1796" @default.
• W2152520153 abstract "The bis(ethylene) IrI complex [TpIr(C2H4)2] (1; Tp=hydrotris(3,5-dimethylpyrazolyl)borate) reacts with two equivalents of aromatic or aliphatic aldehydes in the presence of one equivalent of dimethyl acetylenedicarboxylate (DMAD) with ultimate formation of hydride iridafurans of the formula [TpIr(H){C(R1)C(R2)C(R3)O}] (R1=R2=CO2Me; R3=alkyl, aryl; 3). Several intermediates have been observed in the course of the reaction. It is proposed that the key step of metallacycle formation is a CC coupling process in the undetected IrI species [TpIr{η1-O-R3C(O)H}(DMAD)] (A) to give the trigonal-bipyramidal 16 e− IrIII intermediates [TpIr{C(CO2Me)C(CO2Me)C(R3)(H)O}] (C), which have been trapped by NCMe to afford the adducts 11 (R3=Ar). If a second aldehyde acts as the trapping reagent for these species, this ligand acts as a shuttle in transfering a hydrogen atom from the γ- to the α-carbon atom of the iridacycle through the formation of an alkoxide group. Methyl propiolate (MP) can be used instead of DMAD to regioselectively afford the related iridafurans. These reactions have also been studied by DFT calculations." @default.
• W2152520153 created "2016-06-24" @default.
• W2152520153 creator A5005220672 @default.
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• W2152520153 creator A5058217052 @default.
• W2152520153 creator A5076412720 @default.
• W2152520153 creator A5078170195 @default.
• W2152520153 date "2012-12-18" @default.
• W2152520153 modified "2023-10-16" @default.
• W2152520153 title "Aldehyde-Assisted Hydrogen Transfer during the Formation of Hydride-Iridafurans from Alkynes and Aldehydes" @default.
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• W2152520153 doi "https://doi.org/10.1002/chem.201202794" @default.
• W2152520153 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/23255495" @default.
• W2152520153 hasPublicationYear "2012" @default.
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