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A reversible Van der Waals complex formation between the electron-deficient fluorinated aromatic ring and N,N-dimethylformamide (DMF) molecules followed by light irradiation resulted in charge transfer (CT) process. The complex was stabilized by ammonium formate and further decomposed to form the C-N bond. Control experiments revealed that the simultaneous S N Ar pathway also contributes to product formation. This methodology is mild, metal-free, and effective for the amination of a variety of substrates. The reproducibility of this methodology was also verified on gram-scale reactions. The CT states were supported by control UV/Vis spectroscopy and computational studies., (© 2021 Wiley-VCH GmbH.)

The methylation of Hg(II) (SCH3 )2 by corrinoid-based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the energies of the mercury 6p1/2 and 6p3/2 orbitals, making them energetically accessible for chemical bonding. In the absence of spin-orbit coupling, the predicted reaction mechanism is qualitatively different. This is the first example of relativity being decisive for the nature of an observed enzymatic reaction mechanism., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)