The reaction of Li[Al(OR)(4)] R = OC(CF3)(2)Ph, 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)] and NO[SbF6] in sulfur dioxide solution

NO[Al(OC(CF3)(2)Ph)(4)](1) and NO[Al(OC(CF3)(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%) NO2 with Li[Al(OR)(4)] followed by extraction with SO2. The unfavourable disproportionation reaction of 2NO(2)(g) to [NO](+)(g) and [NO3](-)(g) [DeltaHdegrees = +616.2 kJ mol(-1)] is more than compensated by the disproportionation energy of 3NO(g) to N2O(g) and NO2(g) [DeltaHdegrees = -155.4 kJ mol(-1)] and the lattice energy of Li[NO3] (s) [U-POT = 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(CF3)(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)(2)Ph)(3)]}(2) 3 was prepared by the thermal decomposition of Li[Al(OC(CF3)(2)Ph)(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)(2)Ph)(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)(2)Ph)(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)(2)Ph)(3)]} units linked via fluorine lithium contacts. Compound 1 is unstable in the SO2 solution and decomposes to yield [AlF(OC(CF3)(2)Ph)(3)](-), [(PhC(CF3)(2)O)(3)Al(mu-F)Al(OC(CF3)(2)Ph)(3)](-) anions as well as (NO) C6H4C(CF3)(2)OH, while compound 2 is stable in liquid SO2. The nu(NO+) in 1 and [NO](+)(toluene)[SbCl6] are similar, implying similar basicities of [Al(OC(CF3)(2)Ph)(4)](-) and toluene.