Chapter 11 (H-NMR) – Primary Notes

• This will draw from book, more in depth conceptualization will be in the Chapter 11++ Notes

Double Bonds
• In the case of double bonds, atoms are fixed, meaning hydrogen will be forced into a
configuration until the double bond is broken. See the below two examples:

• The three methyl groups on the left are equivilant, despite the proximity to chlorine. Why? The
three groups rapidly rotate, resulting in no one methyl group being more deshielded than the
others.
◦ The other molecule has a locked configuration, and as a result, the methyl group closest to
the chlorine will show a greater shift than the other one. Said differently, the cis- methyl
group is more desheilded than the trans- one.
• This can even happen around an effective double bond
◦ This is seen in the below molecule, which has a resonance locked sp2 configuration:

◦ This is of note, as it may not be initally obvious that the two

methane groups cannot rotate around the N-C bond.

• For CH3-, -CH2- and CH groups we are given a ‘base shift’, which
we can add or subtract to to determine the approximate shift of the
attached hydrogens. They are .9, 1.3 and 1.7 respectively.
◦ The shifts are as follows (entire next page).
Next section is about diamagnetic disaptrophy, which you can find more of in the ++ notes. What is of
note in this section though is the following:

• It appears diamagnetic disantophy does not effect the carbons in the ring, giving resonance little
to no effect on C-13 shift.

Electron Withdrawal and Donation

• In regards to deshielding, resonance has a much stronger effect then does electronegativity.

◦ This should strongly be considered with halogens, although iodine has the most weakly bonded
electrons, and a lower electronegativity, it still manages to have the largest deshielding effect. Why?
 ▪ Hard-hard vs. hard-soft interactions – flourine’s valence electrons are the same orbital type as
the rest of the ring, so despite it’s electronegativity, it donates more than iodine due to it’s
compatibility. This strongly weakens the amount of donation that occurs. This occurs as a
gradiant, with the effect being slight in chlorine.

◦ In non-resonance structures, the effect is reversed.