769124-21-2Relevant academic research and scientific papers
The reaction of Li[Al(OR)4] R = OC(CF3) 2Ph, OC(CF3)3 with NO/NO2 giving NO[Al(OR)4], Li[NO3] and N2O. The synthesis of NO[Al(OR)4] from Li[Al(OR)4] and NO[SbF6] in sulfur dioxide solution
Decken, Andreas,Jenkins, H. Donald Brooke,Nikiforov, Grigori B.,Passmore, Jack
, p. 2496 - 2504 (2004)
NO[Al(OC(CF3)2Ph)4] 1 and NO[Al(OC(CF 3)3)4] 2 were obtained by the metathesis reaction of NO[SbF6] and the corresponding Li[Al(OR)4] salts in liquid sulfur dioxide solution in ca 40% (1) and 85% (2) isolated yield. 1 and 2, as well as Li[NO3] and N2O, were also given by the reaction of an excess of mixture of (90 mol%) NO, (10 mol%) NO 2 with Li[Al(OR)4] followed by extraction with SO 2. The unfavourable disproportionation reaction of 2NO2(g) to [NO]3(g) and [NO3]-(g) [ΔH° = +616.2 kJ mol-1] is more than compensated by the disproportionation energy of 3NO(g) to N2O(g) and NO2(g) [ΔH° = -155.4 kJ mol-1] and the lattice energy of Li[NO3] (s) [UPOT = 862 kJ mol-1]. Evidence is presented that the reaction proceeds via a complex of [Li]+ with NO, NO2 (or their dimers) and N2O. NO2 and Li[Al(OC(CF 3)3)4] gave {NO3(NO) 3}[Al(OC(CF3)3)4]2, NO[Al(OC(CF3)3)4] and (NO2) [Al(OC(CF3)3)4] products. The aluminium complex (Li[AlF(OC(CF3)2Ph)3]}2 3 was prepared by the thermal decomposition of Li[Al(OC(CF3) 2Ph)4], Compounds 1 and 3 were characterized by single crystal X-ray structural analyses, 1-3 by elemental analyses, NMR, IR, Raman and mass spectra. Solid 1 contains [Al(OC(CF3)2Ph) 4]- and [NO]+ weakly linked via donor acceptor interactions, while in the SO2 solution there is an equilibrium between the associated [NO]-[Al(OC(CF3) 2Ph)4]- and separated solvated ions. Solid 2 contains essentially ionic [NO]+ and [Al(OC(CF3) 3)4]-. Complex 3 consists of two {Li[AlF(OC(CF3)2Ph)3]} units linked via fluorine lithium contacts. Compound 1 is unstable in the SO2 solution and decomposes to yield [AlF(OC(CF3)2Ph) 3]-, [(PhC(CF3)2O) 3Al(μ-F)Al(OC(CF3)2Ph)3] - anions as well as (NO)C6H4C(CF 3)2OH, while compound 2 is stable in liquid SO 2. The (NO-) in 1 and [NO]+(toluene) [SbCl6] are similar, implying similar basicities of [Al(OC(CF 3)2Ph)4]- and toluene.
