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- W2082643180 abstract "The neutral copper(I) ethylene complex [tBu2P(NSiMe3)2-κ2N]Cu(η2-C2H4) (1) reacts with diazophenanthrone (2), yielding an equilibrium mixture of 1 and 2 with free ethylene and the novel diazoalkane copper(III) complex 3, which represents a stabilized analogue of early intermediates in the mechanism of copper-catalyzed cyclopropanation reactions of electron-rich olefins with α-carbonyl diazoalkanes. Its X-ray structure determination displays square-planar coordination of the formally d8 copper(III) center with a κO:κN-bound diazophenanthrone. The geometry of the coordinated diazoalkane ligand can be directly compared to that of uncomplexed, cocrystallized diazophenanthrone, indicating a formal two-electron ligand reduction upon coordination. LT NMR spectroscopy reveals facile rotation of the diazoalkane ligand in solution even at temperatures below −110 °C. DFT calculations (B3LYP) on the model [H2P(NH)2-κ2N]Cu(N2CHCHO-κN:κO) (4) help to understand the bonding and fluxionality in 3 and predict a small ligand rotation barrier (through the transition state 4⧧), in accordance with experimental facts. For model 4, a low-energy pathway for dinitrogen extrusion and copper(I) carbene formation exists, involving a π-bound carbonyl diazoalkane complex and a carbon-coordinated diazoalkane copper(I) species. This pathway, and thus also cyclopropanation activity, is sterically blocked for 3, making it an isolable species." @default.
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- W2082643180 date "2000-09-09" @default.
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- W2082643180 title "A Fluxional α-Carbonyl Diazoalkane Complex of Copper Relevant to Catalytic Cyclopropanation" @default.
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- W2082643180 doi "https://doi.org/10.1021/om000430y" @default.
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