It is well known that cyanide acts as a carbon and not as a nitrogen nucleophile in

It is well known that cyanide acts as a €œcarbon€ and not as a €œnitrogen€ nucleophile in S_N2 reactions; for example,

How can this behavior be rationalized with the notion that nitrogen is in fact more electronegative than carbon and, therefore, would be expected to hold any excess electrons?

a. Optimize the geometry of cyanide using the HF/3-21G model and examine the HOMO. Describe the shape of the HOMO of cyanide. Is it more concentrated on carbon or nitrogen? Does it support the picture of cyanide acting as a carbon nucleophile? If so, explain why your result is not at odds with the relative electronegativities of carbon and nitrogen.

Why does iodide leave following nucleophilic attack by cyanide on methyl iodide?

b. Optimize the geometry of methyl iodide using the HF/3-21G model and examine the LUMO. Describe the shape of the LUMO of methyl iodide. Does it anticipate the loss of iodide following attack by cyanide? Explain.

Transcribed Image Text:

N=C:CH, -I - :NEC-CH3 + I :NEÇ: Гсн, т