Structure and Characterization of CI3[Al{OC(CF3)3}4]; Lewis Acidities of CX3 and BX3

Prepn. of the title compd. (I) from starting materials CI4 and Ag[Al{OC(CF3)3}4](II) was performed with the complete exclusion of light and with carefully purified diiodine-free CI4, since CI4 decomps. within minutes in soln. in light with formation of I2 and other carbon iodides, and II reacts immediately with I2 to give yet unidentified decompn. products. With these precautions I was prepd. in quant. yield. According to calcns. at the MP2/TZVPP level and estn. of the sublimation and lattice enthalpies in a suitable cycle, we est. that the reaction is exothermic by -33 kJmol-1 in the gas phase and by -127 kJmol-1 in the solid state. In CH2Cl2 soln., I is dark blood red and in situ NMR reactions show only resonance signals for the CI3+ ion (d(13C)= 97 ppm; in SO2ClF: d(13C) = 95 ppm; calcd. value: d(13C) = 106 ppm) and the anion (d(13C) = 121.5 ppm (q); d(27A1)= 38.0 ppm). A CH2Cl2 soln. of I is stable for about 8 to 12 h at ambient temp. and much longer if stored at -30 or -78 DegC. Single crystals that appeared yellow as thin plates but black when thicker were grown at -78 DegC from cooled concd. CH2Cl2 solns. of I. The crystal structure detn. of a dark orthorhombic block of I showed that it contained isolated trigonal-planar CI3+ ions with a sum of I-C-I bond angles of 360.0 Deg (range: 118.8-122.1 Deg0) and Al{OC(CF3)3}4 ions. [on SciFinder (R)]