Journal
INORGANIC CHEMISTRY
Volume 41, Issue 8, Pages 2001-2003Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic025563l
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The cationic iridium(III) complex [IrCF3(CO)(dppe)(DIB)][BARF](2) where DIB = o-diiodobenzene, dppe = 1,2-bis(diphenylphosphino)ethane, and BARF = B(3,5-(CF3)(2)C6H3)(4)(-) undergoes reaction in the presence of dihydrogen to form [IrH2(CO)(2)(dppe)](+) as the major product. Through labeling studies and H-1 and P-31{H-1} NMR spectroscopies including parahydrogen measurements, it is shown that the reaction involves conversion of the coordinated CF3 ligand into carbonyl. In this reaction sequence, the initial step is the heterolytic activation of dihydrogen, leading to proton generation which promotes alpha-C-F bond cleavage. Polarization occurs in the final [IrH2(CO)(2)(dppe)](+) product by the reaction of H-2 with the Ir(I) species [Ir(CO)(2)(dppe)](+) that is generated in the course of the CF3 - CO conversion.
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