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If the plane of the carbon carbon chain is considered as being in the plane of this page, the R groups are located on one side or the other of this plane The two con gurations are usually referred to as R and S, although the Cahn Ingold Prelog priority rules cannot be applied strictly since that requires knowledge of the relative lengths of the two polymer chain segements Without knowledge of the lengths of the polymer chain segments, designation of R and S con gurations can be done only in an arbitrary manner One of the con gurations (Ia or Ib) is designated as R and the other as S The lowercase designations, r and s, are often used in place of the uppercase letters to emphasize this aspect (Other designations of the two con gurations appear in the literature: D and L, d and l, and .

) There are two constitutional repeat units (Sec 1-2c) from a stereochemical viewpoint, one with R con guration for the stereocenter and the other with S con guration for the stereocenter (corresponding to Ia and Ib) These are referred to as the two con gurational base units and have an enantiomeric relationship [IUPAC, 1966, 1981, 1996]..

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The classi cation of a C* in the planar zigzag conformation as chirotopic or achirotopic presents dif culty A stereocenter is chirotopic if it lies in a chiral environment [Eliel and Wilen, 1994; Mislow and Siegel, 1984] A chiral environment is one that is not superposable on its mirror image The literal de nition of the term chirotopic would classify each C* as chirotopic since the two polymer chain segments, and , are not equivalent The nonequivalence of the two chain segments is due to differences in length (There may also be differences in end groups depending on the modes of initiation and termination) However, classi cation of C* as chirotopic implies optical activity, and this is clearly not true from a practical viewpoint Optical activity is a short-range phenomenon with its magnitude determined by the differences in the groups attached to the stereocenter.

(8.12)

The rst few atoms of the two polymer chain segments attached to C* are the same and such stereocenters do not contribute measurably to the optical activity of the polymer The only stereocenters with signi cant optical activity are those at the ends of the polymer chain, but their population is negligible for a high-molecular-weight polymer The sum of contributions from all the stereocenters is such that optical activity is below the limits of detection (This discussion of optical activity excludes optical activity arising from the existence of a polymer molecule exclusively in a chiral conformation, a very rare occurrence except for biological macromolecules; see Sec 8-8b A typical polymer in solution exists in the random-coil conformation Many of the conformations are chiral, but on a time-average basis there are equal numbers of conformations of opposite rotation and the net rotation is zero.

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) Thus, it is more useful to classify stereocenters such as those in Ia and Ib as achirotopic The terms stereocenter, chirotopic, and achirotopic will be used in this text in line with the most recent terminology However, other terms are found in the older literature C* was previously referred to as a chiral or pseudochiral center The term pseudochiral center is based on the same convention used to classify C* as achirotopic instead of chirotopic The terms asymmetric and pseudoasymmetric center are found in much older literature 8-1a-2 Tacticity.

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