930101-78-3Relevant academic research and scientific papers
Bismuth-based cyclic synthesis of 3,5-di-tert-butyl-4-hydroxybenzoic acid via the oxyarylcarboxy dianion, (O2CC6H2 tBu2O)2-
Kindra, Douglas R.,Evans, William J.
supporting information, p. 3052 - 3054 (2014/03/21)
3,5-Di-tert-butyl-4-hydroxybenzoic acid can be made under mild conditions in a cyclic process from carbon dioxide and 3,5-di-tert-butyl-4-phenol using bismuth-based C-H bond activation and CO2 insertion chemistry starting with the Bi3+ complex, Ar′BiCl2, of the NCN pincer ligand, Ar′ = 2,6-(Me2NCH2) 2C6H3. Complexes of the recently discovered oxyaryl dianion, (C6H2tBu2-3,5-O-4) 2-, and the oxyarylcarboxy dianion, [O2C(C 6H2tBu2-3,5-O-4)]2-, are intermediates in the process. Further studies of the oxyarylcarboxy dianion in Ar′Bi[O2C(C6H2tBu 2-3,5-O-4)-κ2O,O′], show that it undergoes decarboxylation upon reaction with I2 and it reacts with trimethylsilyl chloride to produce the trimethylsilyl ether of the trimethylsilyl ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid and the Ar′BiCl2 starting material.
Organobismuth(III) dihalides with T-shaped geometry stabilized by intramolecular N→Bi interactions and related diorganobismuth(III) halides
Soran, Albert P.,Silvestru, Cristian,Breunig, Hans J.,Balázs, Gabor,Green, Jennifer C.
, p. 1196 - 1203 (2008/10/09)
Organobismuth(III) compounds containing (N,C,N)-pincer ligands were prepared and characterized both in solution and in the solid state. Compound RBiCl2 1 [R = 2,6-(Me2NCH2)2C 6H3] was obtained from RLi and BiCl3 (1:1 molar ratio). RBiBr2 2 and RBiI2 3 were obtained by halogen-exchange reactions from 1. Reaction of 1 with MeMgI afforded RBi(Me)I 4. Compound R2BiCl 5, obtained from RLi and BiCl3, is rearranged in solution to 1 and R3Bi. The molecular structures of compounds 1-5 were established by single-crystal X-ray diffraction. All dihalides RBiX2 show a T-shaped CBiX2 core. They are the first stable compounds corresponding to the edge inversion transition state at the bismuth center, stabilized by two strong intramolecular N→Bi interactions in trans positions to each other, which contribute to an overall distorted square pyramidal (N,C,N)BiX2 coordination geometry. The electronic structure of [2,6(Me2NCH2) 2C6H3]BiCl2 (1) was analyzed by density functional theory (DFT) calculations, which provide evidence that the stabilization of the square pyramidal geometry of bismuth is electronic rather than steric in nature.
