475636-41-0Relevant academic research and scientific papers
Synthesis, characterization and thermolysis of phosphinite-borane adducts: Investigation of an unusual thermally-induced phenol elimination reaction
Rivard, Eric,Lough, Alan J.,Manners, Ian
, p. 2966 - 2972 (2002)
The synthesis, characterization and thermolytic behavior of a new class of phosphinite-borane adducts containing the bulky 2,4,6-t-Bu3C6H2O (Mes*O) group is reported, including the description of the first example of a primary phosphinite-borane adduct isolable at room temperature (Mes*O)PH2·BH3 1. Adduct 1 and the phenylated derivative (Mes*O)PhPH·BH3 3 formed highly cross-linked solids, 7 and 8, when heated to 100 and 140 °C, respectively. Characterization of these solids by solid state and solution NMR spectroscopy suggest that both dehydrocoupling (H2 elimination) and Mes*OH elimination occur simultaneously to give the complex products [(Mes*O)xRPHy-BH(2x + 2y + z)]n (R = H or Ph, x + y + z = 1). The tertiary adduct (Mes*O)Ph2P·BH3 5 and the phosphite-borane (PhO)3P·BH3 6 were found to decompose at high temperatures via P-B bond cleavage without formation of the corresponding phenol. These results suggest that the thermally-induced formation of Mes*OH from 1 and 3 occurs via α-elimination from a phosphorus center. Adducts 1, 3, 5 and 6 were also structurally characterized by single-crystal X-ray diffraction.
