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by monomer. The whole polymer chain does not migrate, only the active end of the polymer chain migrates. This follows the principle of least nuclear motions. For the polymer chain to remain at its original coordination site after monomer insertion, all or at least most of the polymer chain atoms must move, speci cally back away from the coordination site. For migratory insertion only the atoms of the rst few repeat units move. This regenerates a vacant site with its con guration opposite from the original vacancy. If propagation continued with this species, the result might be syndioselective propagation. Isoselective propagation requires migration of the polymer chain to its original position with regeneration of the original con guration of the vacant site, often referred to as backskip or back- ip. The chain migrates twice for insertion of each monomer unit, and the overall process can also be regarded as a site epimerization. This mechanism, referred to as the

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Fig. 8-12 Crystal structure of a-TiCl3 . Ti and Cl atoms are represented by large black circles and small empty circles, respectively; vacancies, by open squares. After Corradini et al. [1989] (by permission of Pergamon Press and Elsevier, Oxford).

The IC is a major theoretical tool in the study of robustness and is also the basis of robustness; bound the IC and you have a robust estimator. However, the derivation of the IC depends on taking the limit as the sample size goes to infinity (Hampel et al., 1986, $2); hence we might expect some problems in using it as an applied tool when dealing with particular (finite) data sets. For example, the influence of one point may mask the influence of other points, so that the fitted model may have a sensitivity to the position of certain points that is quite different from that predicted by the IC. While the gradient gives the direction of steepest descent in weight space

Cossee-Arlman mechanism, is based on the observed stereoselectivity and molecular modeling studies [Arlman and Cossee, 1964; Ewen, 1999; Rappe et al, 2000; Resconi et al, 2000] A variation on this mechanism involves a lowering of the transition state barrier to insertion by an a-agostic interaction, speci cally, an attractive interaction between titanium and a hydrogen on the rst carbon attached to Ti Isotactic polymerization depends intimately on the crystal structure of the initiator surface For a coordination lattice, as opposed to a molecular crystal lattice, the crystal contains a number of ligand vacancies in order to achieve overall electrical neutrality of the crystal a-TiCl3 crystals are made up of elementary crystal sheets of alternating titanium and chlorine layers aligned along the principal crystal axis [Natta et al, 1961a,b,c,d] Figure 8-12 is a representation of a portion of the crystal [Corradini et al, 1989].

The titanium and chlorine atoms are represented by solid black and open spheres, respectively The titaniums are at the octahedral interstices of the chlorine lattice while chlorines are hexagonally close-packed Every third titanium in the lattice is missing, that is, there is a vacancy in between pairs of titanium atoms Vacancies are represented by & in Fig 8-12 Polymerization occurs at active sites found on the edges (surfaces) of elementary sheets of the crystal and not in the basal planes This is supported by microscopic observations of polymer growth at the crystal edges [Cossee, 1967; Kollar et al, 1968a,b; Rodriguez and van Looy, 1966] A titanium atom at the surface is bonded to only ve chlorines instead of six because of the imposed requirement of electroneutrality Of the ve chlorines, four are more strongly bonded since they are bridged to other titanium atoms.

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The fth, nonbridged chlorine may be replaced by an alkyl group when the titanium component interacts with the group I III component The octahedral vacancy remains as a vacancy Neighboring metal atoms (bridged by two chlorines) have opposite chirality [Allegra, 1971] The two enantiomeric titaniums can be represented as XXI and XXII where one of.

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