Structural data for classical molecules is updated as new experiments are devised to improve precision and accuracy.
Consider the trifluoromethyl compounds E(CF3)3 where E = P, As, Sb. The following C–E–C angles were determined for gas-phase E(CF3)3 by electron diffraction in the middle of the twentieth century: E = P, 99.6(25)°; E = As, 100.1(35)°; E = Sb, 100.0(35)°. (Berger, R. J. F.; Mitzel, N. W. J. Mol. Struc. , 2010 , 978 , 205).
a. Does the trend in these angles seem reasonable? Explain.
b. A more rigorous electron diffraction gas-phase experiment found a C–As–C angle for As(CF3)3 of 95.4(3)°, that compared favorably to the computationally determined angle of 95.9°. Which of the other two C–E–C angles seems more suspect, and should be reinvestigated using modern techniques? Explain.
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