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• W2024132045 abstract "Dehydrogenation of the dihydride (PNP)IrH2 with norbornylene in the presence of t-butyl methyl ether leads to formation of an iridium(I) Fischer carbene complex, (PNP)Ir C(H)OtBu, by double C-H activation and loss of H2. The square planar pincer-type carbene effects quantitative oxygen-atom transfer from CO2 (1 atm) at ambient temperature to generate t-butyl formate and (PNP)Ir-CO. The iridium carbene reacts similarly with carbonyl sulfide and phenyl isocyanate, causing sulfur-atom and nitrene-group transfer, respectively. In the absence of a hydrogen acceptor, thermolysis of (PNP)IrH2 in t-butyl methyl ether under an atmosphere of CO2 also results in the formation of (PNP)Ir-CO and oxidation of t-butyl methyl ether to t-butyl formate via an iridium carbene. Preliminary mechanistic studies indicate that these reactions proceed through an intermediate four-membered metallalactone." @default.
• W2024132045 created "2016-06-24" @default.
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• W2024132045 date "2008-04-15" @default.
• W2024132045 modified "2023-09-27" @default.
• W2024132045 title "Oxygen-Atom Transfer from Carbon Dioxide to a Fischer Carbene at (PNP)Ir" @default.
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• W2024132045 doi "https://doi.org/10.1021/ja801865c" @default.
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