22658-72-6Relevant academic research and scientific papers
Exploration of the Synthetic Potential of Electrophilic Trifluoromethylthiolating and Difluoromethylthiolating Reagents
Zhang, Jingjing,Yang, Jin-Dong,Zheng, Hanliang,Xue, Xiao-Song,Mayr, Herbert,Cheng, Jin-Pei
supporting information, p. 12690 - 12695 (2018/09/25)
The electrophilicity parameters (E) of some trifluoromethylthiolating and difluoromethylthiolating reagents were determined by following the kinetics of their reactions with a series of enamines and carbanions with known nucleophilicity parameters (N, sN), using the linear free-energy relationship log k2=sN(N+E). The electrophilic reactivities of these reagents cover a range of 17 orders of magnitude, with Shen and Lu's reagent 1 a being the most reactive and Billard's reagent 1 h being the least reactive electrophile. While the observed electrophilic reactivities (E) of the amido-derived trifluoromethylthiolating reagents correlate well with the calculated Gibbs energies for heterolytic cleavage of the X?SCF3 bonds (Tt+DA), the cumol-derived reagents 1 f and 1 g are more reactive than expected from the thermodynamics of the O?S cleavage. The E parameters of the tri/difluoromethylthiolating reagents derived in this work provide an ordering principle for their use in synthesis.
Ligand assisted cleavage of uranium oxo-clusters
Nocton, Gregory,Pecaut, Jacques,Filinchuk, Yaroslav,Mazzanti, Marinella
supporting information; experimental part, p. 2757 - 2759 (2010/09/04)
Dibenzoylmethanate replaces the bridging triflate ligands in uranium triflate polyoxo-clusters and cleaves the U12O20 core yielding the new [U6O4(OH)4(η-dbm) 12] dibenzoylmethanate (dbm-) cluster which slowly dissociates into a monomeric complex. This reactivity demonstrates the importance of bridging ligands in stabilizing uranium polyoxo-clusters.
