Chem 181/281 RLG v. W02 p.

1 of 4
Chem 181/281 Tacticity of Polymers from 1,2-disubstituted vinyl monomers


H H H H
R
R R R
R
R R
R
H
H
H H H
H H H H
H
H H H
R
R R
R
R
R
R R R
H
H
R
R
R
POLYMERS MADE FROM RCH=CHR MONOMERS
isotactic
If we examine the configuration of the carbon atoms circled in green and pink, looking toward the right:
If we again examine the configuration of the carbon atoms circled in green and pink, looking toward the
polymer chain (up and away)
polymer chain
(down and away)
polymer chain (up and away)
In both cases, the clockwise sequence is H-R-polymer. That is, the configuration of adjacent carbon
atoms is the same. So this structure is called isotactic.
R
H
H
2.
syndiotactic
1.
Chem 181/281 Tacticity of Vinyl Polymers, p. 2 of 4)

R H
H R'
H R
H
R'
H R
POLYMERS MADE FROM R'CH=CHR MONOMERS
polymer chain
If the two substituents are not the same (RR'), there are three possible stereoregular patterns: threo-
diisotactic, erythro-diisotactic, and disyndiotactic. Now we revert to the conventional use of "isotactic"
and "syndiotactic" that are used for mono-substituted vinyl polymers.
polymer
chain
polymer
chain
When the R groups on adjacent monomer unitsare all on the same side, and the R' groups are also
all on the same side, we have a diisotactic structure. In order to see how the threo and erythro
designations arise, we must first look at how those terms are defined. The following diagrams show
the (eclipsed) Fisher projections and the corresponding Newman projections, first eclipsed ( cis backbone),
then rotated as it would be if the polymer had an all transbackbone conformation.
THREO
H R'
H
R
polymer
chain
polymer chain
R' H
polymer
chain
R
H R
H R
H
R
polymer
chain

H
R' H
R'
H
polymer chain H
polymer chain
R'
R' H
polymer
chain
polymer
chain
ERYTHRO
polymer
chain
Fisher projection
Newman projection
Chem 181/281 Tacticity of Vinyl Polymers, p. 3 of 4)
H H H H
H
H H H
H
R
R R
R
R'
R'
R' R' R'
H R H
R
threo
polymer
chain
Newman projections showing the threo
If we now examine the diisotactic structure below, and draw the Newman projection for the two
carbon atoms circled with the green (left) ellipse, we see that the Newman projection at left
matches the threo arrangement, in that R and R' are on the same side. If we chose the carbons
circled with the pink ellipse, we get the Newman projection shown at the right. Again, both R and
R' are on the same side.
polymer
chain
3a.
diisotactic
H
R'
H R'
polymer
chain
polymer
chain
H H H H
R'
R' R' R'
R
R R
R
H
H
H H H
Now examine the diisotactic structure below, and draw the Newman projection for the two
carbon atoms circled with the green (left) ellipse. We see that the Newman projection at left
matches the erythroarrangement, in that R and R' are on opposite sides (anti-periplanar). If we
chose the carbons circled with the pink ellipse, we get the Newman projection shown at the right.
Again, both R and R' are on opposite sides (anti).
erythro
arrangment.
arrangement.
R'
3b.
H
R
diisotactic
polymer
chain
polymer
chain
Newman projections showing the erythro
H R
arrangment.
arrangement.
Chem 181/281 Tacticity of Vinyl Polymers, p. 4 of 4)
H R H R
H
R' H R'
R
H R
H
H
R'
H R' H
H R'
R
H
disyndiotactic
polymer
chain
polymer
chain
Newman projections showing alternating thre
and erythro arrangements.
R
R'
The disyndiotactic structure is shown below. Notice that the R groups are on alternating sides in
adjacent monomer units, and the R' groups alternate as well. Hence the name disyndiotactic.
TheNewman projections that result from selecting the carbons in each of the two ellipses are
shown below.
polymer
chain
polymer
H
H
4.
Notice that the configurations at adjacent carbons alternate (threo, erythro). By simply
moving our ellipse one carbon to the right, we observe the opposite stereochemistry. We could not
distinguish between erythro and threo unless the polymer chain ends were distinguishable. Generally,
for long polymer chains, we treat the "ends" (the 'polymer chain' label in our Newman projections)
as identical. If this is so, then we can only describe one stereoregular disyndiotactic arrangement
that arises from R'CH=CHR monomers. The erythro and threo designations have no meaning.
chain

R'
o