The electronic spectra of mixtures of CH2C12 solutions (each 0.993 mmol dm 3) of I2 and the donor D shown in the diagram on the next page were recorded for different volume ratios of the two solutions. Values of the absorbance for the absorption at Amax = 308 nm are as follows:
Volume ratio 12 :D | Absorbance |
0:10 | 0.000 |
1:9 | 0.056 |
2:8 | 0.097 |
3:7 | 0.129 |
4:6 | 0.150 |
5:5 | 0.164 |
6:4 | 0.142 |
7:3 | 0.130 |
8:2 | 0.1O3 |
9:1 | 0.070 |
10:0 | 0.000 |
Data: A..I. Blake et at. (1997) .j. Chem, Soc.. Dalton Trans., p. 1337.]
(a) Suggest how compound D might interact with I2.
(b) Use the data in the table to establish the stoichiometry of the complex formed between D and I2. Why can the absorbance data be used for this purpose?
(c) In the Raman spectrum of the complex, a band at 162cm-1 is assigned to the I2 stretching mode. Explain why this value is shifted from that of 215 cm 1 for l2 itself.
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