96236-02-1Relevant articles and documents
Switching the Spin State of Diphenylcarbene via Halogen Bonding
Henkel, Stefan,Costa, Paolo,Klute, Linda,Sokkar, Pandian,Fernandez-Oliva, Miguel,Thiel, Walter,Sanchez-Garcia, Elsa,Sander, Wolfram
, p. 1689 - 1697 (2016/02/20)
The interactions between diphenylcarbene DPC and the halogen bond donors CF3I and CF3Br were investigated using matrix isolation spectroscopy (IR, UV-vis, and EPR) in combination with QM and QM/MM calculations. Both halogen bond donors CF3X form very strong complexes with the singlet state of DPC, but only weakly interact with triplet DPC. This results in a switching of the spin state of DPC, the singlet complexes becoming more stable than the triplet complexes. CF3I forms a second complex (type II) with DPC that is thermodynamically slightly more stable. Calculations predict that in this second complex the DPC?I distance is shorter than the F3C?I distance, whereas in the first (type I) complex the DPC?I distance is, as expected, longer. CF3Br only forms the type I complex. Upon irradiation I or Br, respectively, are transferred to the DPC carbene center and radical pairs are formed. Finally, on annealing, the formal C-X insertion product of DPC is observed. Thus, halogen bonding is a powerful new principle to control the spin state of reactive carbenes.
SOLVOLYTIC STUDIES OF THE HIGHLY CROWDED 1-ARYL-1-PHENYL-1-(TRIFLUOROMETHYL)METHYL BR0MIDE AND TOSYLATES
Liu, Kwang-Ting,Kuo, Mann-Yan
, p. 355 - 358 (2007/10/02)
In the titled system the remarkably high tosylate/bromide solvolysis rate ratio of 1.56E6:1 indicates a highly strained ground state, and the reverse order of reactivity for substrate having l-(4-trifluoromethyl)phenyl vs. that having 1-(3-trifluoromethyl
