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CO2 conversion to phenyl isocyanates by uranium(vi) bis(imido) complexes.

  • Author(s): Maria, Leonor
  • Bandeira, Nuno AG
  • Marçalo, Joaquim
  • Santos, Isabel C
  • Gibson, John K
  • et al.
Abstract

Uranium(vi) trans-bis(imido) complexes [U(κ4-{(tBu2ArO)2Me2-cyclam})(NPh)(NPhR)] react with CO2 to eliminate phenyl isocyanates and afford uranium(vi) trans-[O[double bond, length as m-dash]U[double bond, length as m-dash]NR]2+ complexes, including [U(κ4-{(tBu2ArO)2Me2-cyclam})(NPh)(O)] that was crystallographically characterized. DFT studies indicate that the reaction proceeds by endergonic formation of a cycloaddition intermediate; the secondary reaction to form a dioxo uranyl complex is both thermodynamically and kinetically hindered.

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