Chemistry 303 Lecture 12 Fall, 2012 1

Infrared Spectroscopy: detector of functional groups

Stretching vibrations for multiple bonds and single bonds to H absorb in the region 4000-1500 cm-1.

Single Bond stretch, bends, combinations are of lower energy and appear in a complex region 1500-600 cm-1:
fingerprint region

"SUPERIMPOSABLE" IR spectra is acceptable proof of identity for two samples.

Intensity of the absorption depends of the dipole moment change during the vibration:
More polar bonds give greater intensity.
Vibrations with no dipole change show no peak.

Most common: correlate absorption due to bond stretching with local structural features
( presence of functional group, types of C-H, types of C=O)

Depends on bond strength (single, double, triple; relative s character)

NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY:

Discussion: http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/nmr/nmr1.htm#nmr1
Data: http://riodb01.ibase.aist.go.jp/sdbs/cgi-bin/direct_frame_top.cgi
Spectral problems: www.chem.ucla.edu/webspectra/ Beginning #1, 3, 4, 6, 9, 11, 12, 20, 25

Most important means of structure determination for organic compounds

Nuclei have spin: 1H has spin 1/2

magnetic moment,

from QM--spin 1/2 leads to two opposite orientations of

spin axis. You can think of up/down

Bo
 Chemistry 303 Lecture 12 Fall, 2012 2
for 2H (deuterium): spin = 1 (3 orientations)

for 11B spin = 3/2 (4 orientations)

Many common nuclei have spin 1/2: 13C, 31P, 19F Some are zero: 12C, 16O
Some are 1: 14N, 2H (deuterium)

For isolated nucleus, no energy difference between the orientations. But add magnetic field, Bo

Now, the axis can be aligned or opposed and there is an energy difference, , between them.

With nuclei having nuclear spin (e.g., 1H) and in a strong magnetic field, can irradiate with h =
Absorption of this energy allows the nuclei to change spin orientation, spin flip from lower energy orientation to
higher energy orientation.

Higher applied field, Bo, higher .

 Chemistry 303 Lecture 12 Fall, 2012 3
Convenient field: about 85,000 gauss. = 10-5
kcal/mol (very small)
= 1 m (radio)
= 360 X 106 Hz (360 megahertz, 360 MHz)

Can range from 300 MHz/70,000 gauss to 900 MHz/210,000 gauss

The NMR machines are on the B floor of Frick. All of them use superconducting magnets in order to get
high magnetic fields. You will see the shiny metal cylinders which are basically "Thermos bottles" to contain
the liquid helium in which is immersed the wire coil that is the magnet, and then down the center of that goes
the sample tube. The sample is insulated from the helium, and is at room temperature. The magnetic fields are
high enough that you do not want to go near them with things like watches or magnetized strips (credit cards,
etc). They run at 400 MHz, 500 MHz, and 600 MHz. Recently added 3 more machines, all at 500 MHz.

The highest available operates at 900 MHz, at a cost of $2-3 Million.

The stronger the magnetic field, the bigger the difference in frequency for two different H.

For electromagnets, the magnetic field depends on the current running through the wire coil.

Beff
= = gyromagnetic ratio (characteristic of nucleus, independent of
2
environment, temperature, etc)
Beff = actual magnetic field felt by nucleus (not Bo)

But: if Beff is the same for all H in a molecule, get same E, same frequency of absorption.
Scan , get one peak, absorption at one : H detector.
 Chemistry 303 Lecture 12 Fall, 2012 4
However, there are many circulating electrons in bonds; Bo induces a local B around bond to H.

Different bond types lead to different local B. The local field opposes the applied field: B reduces Bo.
Said to "shield" (a little) the nucleus from the applied field

So Beff = Bo - Bo Shielding is proportional to the applied field.

= shielding constant, depends on local environment (number and types of bonds)

Small effect: for = 600 x 106 Hz, the various types of H in organic molecules give shielding
which corresponds to 0-6000 Hz!

CONSTANT FREQUENCY: More shielded protons induce a stronger local induced field,
absorb at higher Bo

Need to raise Bo to compensate for shielding by local field. More shielded = higher field for absorption
When the exact match is reached, energy is absorbed and the nucleus is said to be "in resonance".
 Chemistry 303 Lecture 12 Fall, 2012 5
CONSTANT MAGNETIC FIELD: vary the frequency of the microwave source.
Now lower frequency corresponds to more shielded proton (weaker Beff )

In practice, label the horizontal axis in units of frequency

Not easy to measure absolute position of the absorption signal.

Use relative position compared to the absorption signal of a standard.

Accepted historical standard: tetramethylsilane (TMS) is 0 Hz.

12 H in equivalent environments, one signal or peak.

Very shielded, far "upfield" and generally not overlapping

with regular organic compounds.
Intensity

TMS

480 420 360 300 240 180 120 60 0 (Hz)

Stipulate # Hz downfield from TMS as the "chemical shift" of a proton or set of equivalent protons
 Chemistry 303 Lecture 12 Fall, 2012 6
Consider: Ha
Hb At 600 MHz 600,000,000 Hz
Ha C O (140,000 gauss)
Ha
Intensity

TMS

4800 4200 3600 3000 2400 1800 1200 600 0 (Hz)

8 7 6 5 4 3 2 1 0 (ppm)

For simplicity: at 600 MHz Ha is at 2100 = 3.5 x 10-6 ( 3.5 ppm)

600 x 106

Call the relative position the "chemical shift", measured in ppm relative to TMS, referred to as

Ha
a = machine

Chemical shift depends on shielding; related to inductive effect and pi orbital effects

Depends on how many other H on the same carbon:

0.9
CH3
H3 C C C CH3
H2 more substituted carbon, less shielded
H
0.9
1.3 1.6

Empirical correlations
 Chemistry 303 Lecture 12 Fall, 2012 7
General rules:

a. Inductive effects: O

H3C SH H3C OH H3C O S F (fluorosulfonate)

O
2.5 3.5 4.2

more EN atom attached higher for attached H

H H H H
H C H H C H H C Cl Cl C Cl
ca 2 ppm per Cl
H Cl Cl Cl
a effect
0.8 3.5 5.5 7.3

Much smaller effect in position; no effect beyond

X X effect: 0.53/Cl
C C C C
H

b. pi bonds/hybridization

pi bonds give strong local shielding effects--depends on exact geometry of H.

H
H H
2.4
What's going on?
5.5-6.5 7-8
 Chemistry 303 Lecture 12 Fall, 2012 8

H H
H C O
C C H
H H

H 2.5

C
H
7.2 C

R
 Chemistry 303 Lecture 12 Fall, 2012 9

H continuous circle of pi bonds: an annulene

[18]-annulene

Additivity table for prediction of chemical shift positions for sp3-type hydrogens
Not H on alkenes, arenes (benzene), aldehydes.

Refer to Additivity Table, and learn to use it. [NMR supplement, p 6]

Consider:

O CH2
-CH2- std
H3 C - C=O
CH3
-C=CH2
H H
predict ______
observed: 3.11
 Chemistry 303 Lecture 12 Fall, 2012 10
Peak intensities:
Generally the area under a peak is proportional to the
# of equivalent Hs

Example: CH3OCH2OCH3
Intensity

8 7 6 5 4 3 2 1 0 (ppm)

Integration: vertical distance is proportional to area

Complication from spin-spin splitting:

Consider 1-chloro-2-propanone: in CDCl3 at 300 MHz

H2
C CH3
Cl
O
 Chemistry 303 Lecture 12 Fall, 2012 11

Consider the spectrum of propanoyl chloride in CDCl3

Predict a peak at 3.0 of area 2. Peak at 1.2 of area 3.

H2
C Cl
H3C
O

Coupling of H on adjacent carbon atoms.

Referred to as spin-spin splitting

Most common for H on adjacent carbons.

HA HB HA HB HA HB HA HB
Intensity

8 7 6 5 4 3 2 1 0 (ppm)

Distance between the peaks in (Hz) is the "coupling constant" [J in Hz],

 Chemistry 303 Lecture 12 Fall, 2012 12
NOW:
H2
C Cl
H3C
O
HB sees: 3 HA
HA sees: 2 HB
1:3:3:1
equal

equal
Intensity

8 7 6 5 4 3 2 1 0 (ppm)

n+1 rule: In general, H adjacent to n equivalent protons gives

(n + 1) peaks in the ratio predicted from the polynomial expansion. (n+1)2, (n+1)3, etc

Or: Pascal's triangle:

 Chemistry 303 Lecture 12 Fall, 2012 13

Cl CH3
H2C O
C CH3 Doublet,6H
1.14 ppm,
H J=7Hz

Singlet, 3H,
2H, 5.48 ppm

Septet, 1H, 3.2, J=7Hz

6 5 4 3 2 1 0
PPM

Magnitude of the splitting:

C H on same carbon (geminal) large J 10-20 Hz for sp 3-H

but depends on angle (hybridization)
H

Depending on angle

adjacent (vicinal) 2-10 Hz

H H
For unrestricted rotation, J = 7 Hz (very common)

H on non-adjacent C J = 0 or nearly 0 (special cases: 1-2 Hz)

[Special effects of bonds: See Table of coupling constants]

 Chemistry 303 Lecture 12 Fall, 2012 14
Special cases:

Equivalent "geminal" H as in CH3-Cl appear as singlet. Why not show large coupling?

This is extreme case of a special effect. "Second order"

As difference in between coupled protons become smaller

(and similar in magnitude to J), spectrum changes form:

A - B
If < 20
JAB
HA HB
Begin distortion from simple













doublets or doublets

HH HH
For X = Y, single peak
For X very different from Y, two triplets
X Y For X similar to Y, complicated by second order effects.
 Chemistry 303 Lecture 12 Fall, 2012 15

Beyond recognizing that 2nd order effects are operating, need not analyze in detail.

Analyze the simple patterns (perhaps somewhat distorted) predicted by polynomial expansion.
Be able to determine , J, and relative areas from 1st order spectra.
Be able to determine areas and assign approximate chemical shifts to "multiplets" in 1st or 2nd order spectra.
Chemistry 303 Lecture 12 Fall, 2012 16