Mechanism, Stereochemistry and Applications of Homogeneous Ziegler-Natta Polymerization

T. Wilson SED Group Meeting Jan. 27th 2008

Poly-Olens in Industry and Society

Poly-olens -Fastest-growing segment of the polymer industry -World-wide production is in excess of 160 billion pounds/ year The three major classes of polyethylene: -High density polyethylene (HDPE) is a linear, semi-crystalline homopolymer of ethene -Linear low-density polyethylene (LLDPE) is a random copolymer of ethylene and alpha-olens -Low density polyethylene (LDPE) is a branched ethylene homopolymer Uses of Poly-olens -Vary from asphalt blends and sealants (amorphous) to surgical prostheses (Linear, Ultra-HDPE)

Polymer Properties
Polymer tacticities, connectivities, and lengths
Connectivity Stereochemistry

Me

Cat.

Regio-irregular

Isotactic

Syndiotactic (antiotactic) Regio-regular

x y

Degree of Polymerization
n m

Isotactic-Atactic Stereo-block

Atactic

- Goal of modern polymer chemistry is to control all factors of a polymers microscopic structure

Historical Work of Ziegler and Natta

Early polymerization w/ aluminum: The Aufbaureaktion
Al(Et)3 H2C CH2 (100 atm.) 100 C (C2H4)m-C2H5 Al (C2H4)n-C2H5 (C2H4)o-C2H5 m,n,o < 100 O2, H2O HO (C2H4)m-C2H5 m = 6-8

- Large scale production of detergents

Ziegler, K et. al. Angew. Chem. 1955, 67, 425

Polymerization of ethylene
H2C CH2 EtAlCl/TiCl4 1-5 atm, 23 - 60 C n

-high molecular weight, Linear PE -low pressures and temperatures

Natta!s Contribution
EtAlCl/VCl4 1-5 atm, 23 - 60 C
Natta, G. et. al J. Am. Chem. Soc. 1955, 77, 1708.

-1st example of a crystalline isotactic polypropylene

Nobel Prize in Chemistry to Ziegler and Natta in 1963

combination of tetravalent and trivalent titanium is necessary for high activity; this question is under active investigation. These results shed considerable light on the puzzling behavior observed in our early work. Undoubtedly, oxygen reacts with the trivalent titanium species to oxidize it to a tetravalent form. Synthesis of Ti(III) metallocene/Al complex This reacts with the alkylaluminum compound to form an active catalyst, which probably is Solid (Air Sensitive) Heptane reduced; ;.e.,Blue an Crystaline oxidation-reduction system is set Cl Ti -EA, EPA, and Colorimetric Analysis Cl Al compound is too highly active, Cold Cl up. If the alkyl suggest Ti(III)/Aluminum complex it either reacts with the oxygen preferentially or (C5H5)2Ti(III)Cl1/2(C2H5)2AlCl1/2C2H5AlCl2 reduces the Ti(1V) too rapidly and a good catalyst does not result; this serves to explain the variable H2C CH2 (g) results with triethylaluminum, which reacts with w/ 0.025 mol% O2 oxygen very rapidly. Cl Cl Al Ti It is our Cl 1 L Toluene, 15 C, 1h belief that n the active catalyst is a species such as-174 (CsH&TiEtCl.EtAlCL or a reg PP 5 mmol action product of this activity with to ethylene, and that the 10 mmol -Similar Ziegler Catalysts -Linear polymerof (0.05% Methyl content) polymer grows by insertion a monomer molecule between the alkyl group and the titanium. The - Authors propose that oxygen

Homogeneous Metallocene Catalysts

C1 C2Hs CI C,Hi, oxidizes the Ti(III) to the active a+/ \6-/ ,/ / ~ C ~ H , ) , T I AI-CI + (CsHs)>T1 AI-CI Ti(IV) catalyst \ \ - Raises question of the role of C4Hr CI the aluminum activator - Earliest example of first step in the polymerization would probably inhomogeneous metallocene cat. Breslow, D et. al. JACS, 1959, 81, 81.

'

volve a n-type complex between the titanium and the olefin; if our structure is correct, the aluminum

(13) Natta and co-workersev" have indicated recently that soluble

Intermittent-Growth Model
Kinetic studies of Reichert, Fink and Eisch - Kinetic studies on alkylaluminum activated metallocene catalysts revealed that polymer growth alternated b/w dormant and active states. REVIEWS - Lead to the development of the intermittent-growth model
C'-P,-,
) I :
)

C'-P,

=
+

C P ',

Al2 = (AlEtCl)2 Al' = (unknown) Pn = Polymer chain C = Inactive state C* = Active state

C-P,-,

c-P,
Riechert, K. H. angew. makromol. chem. 1970, 12, 175

Cp Cp

Scheme 4. "Intermittent-growth" model involving equilibria between polymerbearing. but inactive (C-P,) and active catalyst species (C*-P.), Dormant primary complexes Active Cl generated halide, as proposed by Fink and co-workers Cl Cl Pn alkykdlumlnum Cl2AlEt byCexcess Pn+1 Cl H2C CH2 Cp Cp p M Al Et Pnpolymer M AlAl; M [31]. AI2 = (AIEtCl,),, . = chain withn monomer units; Et = unknown. P Al Et Cl C C p C Cl p Cl p Cl Cl C-P,, here Cp,TiP,,CI ' .ClAICI,Et. Cl
'

Lewis Acid/Base Adduct

Tight ion pair

Activator-Free Polymerization
Study by Jordan and co-workers
BPh4 Zr Me Me Ag[BPh4] Zr Me NCMe (AgMe) not obs. Ag0
J . A m . Chem. SOC. 1986, 108,

C2H6

80% yield

THF
'11

In C erizatio activity 1-4 atm presenc ethylen donor l THF o The original erizatio a neces the acti absence spectro

Activity towards polymerization of ethene Figure 1.

C2H4 (4 atm.) [Cp2Zr(Me)(THF)][AgBPh ]
DCM, 23 C, 1h

1'7

Structure of the Cp,Zr(CH,)(THF)+ cation. The BPh4structure is normal. Important bond lengths (A) and bond angles (deg) are as follows: Zr-C(35) 2.256 ( I O ) ; Z r - O 2.122 (14); Zr-Cp(av) 2.487 (41); Zr-CNT(av) 2.174; O-C(36) 1.443 (27); 0-C(39) 1.464 (25); 4 CNT-Zr-CNT 129.6; C(35)-Zr-0 97.4 (5); C(39)-0-C(36) 104.5 (16); C N T indicates the centroid of a C p ring.

Ackn donors Americ Researc X-ray d CHE84

-Activity of ca. 0.2g/(mmol cat.)

Reduced activity attributed to ligand exchange b/w ethene and THF

Jordan, R. F. JACS 1986, 108, 7410.

Supp collecti [Cp2Zr isotropi tropic t thermal structu any cur

(23) T = 18400 (24) T generate CP,Z~( trapped a

of a few minutes. The ra characterized by La, = 39 concentration of the react of ethylene with formation of p~lyethylene'~~! Addition of If trimethylaluminum pr methyltitdnium(lV), trimethylaluminum.traces and of chloride in the form of bis(cyclopentadieny1)titaniin the presence of propy um(1v) chloride lowered the yield of polyethylene, initiated -~ starting compound is obse the known reduction reaction to the expected extent and O n removal and replacem Amount of Re1 Mol Wt accelerated it[s1. O n the other hand, the yield increased to wdter ddded (viscometric) the maximum arises at 3 600000 g polyethylene/g titanium and the activity to 400000 g Interesting observation by Kaminsky and Sinn [mol~l] ethylene ensues. That is, t polyethylene/g titaniumlh when one equivalent of trimethyl~ ~ _ _ _ observed simultaneous presenc or triethylaluminum previously treated with water was-Best addedactivityon 0 . 2 5 x 10-2 3 800000 C H (7.9 atm) for Al/H2O ratios of 2:1 to 2 4 dienyl)titanium(iv) with w to dialkylbis(cyclopentadienyl)titanium(~v) [alkyl, e. g. methyl] 4.6 x l o - ' 200000 H O 5:1 2 Me ethylene (Fig. 1 c). (cf. Table 1 and example 1). Ti 4.6 x I 0 90000 AlMe3 n - For Al/H2O ratio of 1/3 Me Toluene, 21 C 7.5 x 10 ' activity dramaticallytrimethylaluminum. drops an Table 1 tthylene polymerization with the system bis(cyclopentddienyl)dimethyltitdnium(lV),

dienyl)titanium(iv) with water-treated trialkylaluminum and NMR-spectroscopic investigation of such a reaction in the ethylene (Fig. 1 c). presence of ethylene revealed a weak but lasting insertion

The Role of Water: MAO Activators

~~ ~ ~

~~

~~~

Rater
~~

.~

~~

~~

~~

Yield of polyethylene

[gill

Time [h]
~~~

Temp

["CI
21 21 50
I2

._____~
~~~

d e e g

33.6 43.2 57.6 34.2

I12
I.5

-~
~~

Tltdnium concentration [mol 'I]

~~ ~~ ~

Amount of wdter ddded [mol~l]

~ ~ _ _ _

Re1 Mol Wt (viscometric)

~

I .5 1.5

7 x ~ o - ~ 7 x10-4 3.5x 1 0 - J
1.1 x 10-6

i0.25 x 4.6 x 4.6 x 7.5 x

~~~

10-2 lo-' I0 10 '

3 800000 200000 90000

~

UV Data for rxn: A1:Interestingly, 1.5 M Cp2Ti(Me) compounds 2 in Tol. formed on the basis of bis(cyclopentadienyl)zirconium(Iv) and exhibiting no polymerization A 2: A1 + 14.4 mmol Al(Me)3

Authors attributed increased activity to the formation of catalysts by addition of trialkylaluminum previously treated A after 25 minutes with water. These systems excel in that products with relative 5: A4 methyl aluminoxanes (MAO)
activity -even in the case of completely dehalogenated secondA : A1 + Al(Me) pre-treated w/H O 3 3 2 ary p r o d u c t ~ [ ~ ~ - c aalso n become very active polymerization A4: A3 in the presence of C2H4 masses between a few million and a few hundred can be generated at almost constant activity by suitably choosing the reaction Kaminsky, W.temperature et. al. Angew.(Table Chem. 2). Int. Ed. Engl. 1976, 15, 630.

Fig. I . U V spectroscopic measurements (Car) IJI. Tahle 2. Control of molecular weight by choice of temperature i i i the polymeri7ation of ethylene with tri(cyclopentadienyI)rirconium a ) Curve A , : 1.5 mmol Cp2Ti(CHr)2'litertoluene. Curve A 2 : A , + 13.4 -aluminum com-

MAO Activators (The Black-Box)

- Prepared by the control hydrolysis of trimethylaluminum - Exact structure and composition are not well understood

1D linear or cyclic chains (3-coordinate Al)

2D-cyclic structures (3- and 4-coordinate Al)

3D-clusters (3- and 4-coordinate Al)

- Multiple equilibria present in solution further complicate matters

-Generally accepted that the mechanism of activation involves abstraction of a chloride (L2ZrClMe) or a methyl anion (L2ZrMe2). - Large excesses are need (>200/1, Al/Ti)
Marks, T. et. al. Chem. Rev. 2000 100, 1391.

Cation-Like Homogeneous Polymerization

Study by Marks on Cation-like homogeneous Zr-Catalysts
Me Me Zr Me Me Me Me 3624 J . Am. Chem. SOC.,Vol. 113, No. 9, 1991 B(C6F5)3 Benzene [1,2-(CH3)2C5H3]2ZrCH3

+ CH B(C F ) 3 6 5 3

Crystalline solid characterized by EA, MS, NMR and X-Ray

Communications to the Editor

(C6FJ),-(2). Important distances1991 (A) and angles (deg) are as Marks, T. et.bond al. JACS, , 113, 3623 follows: Z r C ( 1 5 ) = 2.252 (4), Z r C ( 3 4 ) = 2.549 (3), B C ( 3 4 ) = 1.663 (5), Zr-H(34A) = 2.71 (3), Zr-H(34B) = 2.25 (3), Z-H(34C) = 2.30 (3), Z r C d n g= 2.500 ( I ) (av), C(15)-ZrC(34) = 92.0 (I), Zr-C(34)-B = 161.8 (2), ring centroid-Zr-ring centroid = 131.3 ( I ) , C(16)-B-C(34) = 108.7 (3), C(22)-B-C(34) = 112.7 (2), C(28)-B-C(34) = 102.8 (3).

Figure 1. Molecular structure of [ 1 ,2-(CH,)2CSH3]2ZrCH3+ CH,B-

Key Distances: as evidenced by the high-temperature interchange of the diasteZr-C(15): inversion (2.280 for 2) reotopic ring2.273 signals, of Cp the2ZrMe dissymmetric ion pair structure occurs at a slightly greater rate (AG* = 18.3 (2) Zr-C(34): 2.549 (2.249 for other !CH3) kcal/mol (80 "C)) in 2. B-C(34): 1.663 (normal) The crystal structure of 215 (Figure 1) consists of a 'bentZr-H(B):[ 1 2.25 (2.16 for other agostic H's) sandwich" ,2-(CH3)2C5H3]zZrCH3+ cation weakly coordinated to a CH3B(C6F5)3anion via a nonlinear (161.8 (2)O), highly Key Angles:Zr(p-CH3)B bridge. With the exception of a unsymmetrical shortened Zr-C(l5) bond (cf., 2.273 (9, 2.280 (5) A in CpzZr-C(34)-B =161.8 Zr(CH3)2),16J7 key aspects of the Zr coordination sphere such C(16)-B-C(34) = 108.7 as the angle ring centroid-Zr-ring centroid and Zr-C",,&av) are C(22)-B-C(34) = 112.7, unexceptional (132.5O and 2.525 (12) A, respectively, in C(28)-B-C(34) = 102.8 Cp2Zr(CH3)z16J7). The Zr-CH3(bridge) distance is elongated byC(16)-B-C(22) ca.0.3 & I 8 while= the B-CH3 106.5 distance appears to be norma1,I" and the valence angles about B deviate only slightly from tetraC(16)-B-C(28) = 114.3 hedral. The C(34) hydrogen atoms are bent away from B and C(22)-B-C(28) = 112.0. toward Zr, with the closest Zr-H contact (2.25 (3) A) exceeding typical terminal and bridging Zr-H bond distances (1.78 (2) and 1.94 (2), 2.05 (3) 9I)&. as well as a short Zr-.H(C,,,,) *agostic" distance (2.16 A).2o Complexes 1-3 are active homogeneous catalysts for olefin polymerization. Using procedures described previously,21 ethylene polymerization proceeds rapidly at 25 OC, 1 atm pressure, with NJ1) = 45 s-I (-4.5 X lo6 g of polyethylene (mol of Zr)-I h-' atm-I), roughly comparable in activity to typical zirconocene/ alumoxane catalysts.lfJ The polyethylene produced is highly linear by NMR22with relatively high molecular weight (A?, = 124000, Xfn = 61 200).23 With propylene2I at 25 OC, 1 yields atactic (by

-Highly unsymmetrical bridging methyl -Shortened Zr-C(15) bond -Boron distance/angles are typical

Cation-Like Homogeneous Polymerization

Polymerization of ethylene and propylene
H2C CH2 Zr-Cat. Toluene, 23 C, 0.5 h n

(1 atm)

- 4.5 x 106 g PE (mol of Zr)-1 h-1 - Similar to activity observed with MAO/Zirconocene catalysts
1.4 mM Zr-Cat. Toluene, 23 C, 0.5 h

(5 atm)

-Provides direct experimental evidence for abstractive role of group 13 co-catalysts/activators in Ziegler-Natta polymerization

- 2.1 x 104 g PE (mol of Zr)-1 h-1 - atactic Polypropylene - NMR control experiment showed that >70% of Zr-cat. undergoes olen insertion

Marks, T. et. al. JACS, 1991, 113, 3623

Mechanism of Ziegler-Natta Polymerization

Cossee mechanism (1960)

Cossee, P. Tetrahedron Lett. 1960, 17, 17.

-Can also have a 2,1-insertion (regio-irregular)

Key Features: - Olen insertion via cis-opening of the double bond - For prochiral olens, insertion occurs such that non-bonding interactions are minimized (R-groups are trans in the T.S.)

Modied Cossee mechanism (Brookhart-Green-Rooney)

agostic: derived from a greek word, which appears in Homer (trans: to hold or clasp oneself)

Evidence For Agostic Interactions

Kinetic isotope effects in hydrodimerizations Mechanism is similar to Z-N Polymerization
Cp2ZrCl2/MAO H2 R Cp Cp R Zr H (Cp2)Zr H H R R (Cp2)Zr R H H R R (Cp)2Zr - [(Cp)2Zr-H] R H3C H2 R R Higher oligomers

Hydrodimerizations of deuteriohexene (Brintzinger)

(E)- or (Z)-1-deuteriohexene Cp2ZrCl2 (0.1mol%) H2 (15 atm), MAO Toluene, -5 C, 20h D n-C4H9 n-C4H9 n-C4H9 D n-C4H9

CH2D CH2D anti (threo) syn (erythro) 5% yield (anti : syn = 1.3 : 1)

Brintzinger, H-H. Angew. Chem. Int. Ed. Engl. 1990, 102, 1412

Evidence for Agostic Interactions

- Observed selectivity could be explained by agostic interactions
Cp2Zr H H R D H (E)-series
Cp2Zr H D R H H (Z)-series

Cp2Zr !-H agostic H Cp2Zr H D D CH2R R H kH H Cp2Zr H D D CH2R R H H2 H H2DC D CH2R R H D H D

H R H !-D agostic D Cp2Zr D H H H R kD D Cp2Zr D H CH2R H R H2 H CH2R

Cp2Zr H D !-H agostic H D H R kH H Cp2Zr H D

Cp2Zr D H

H R H !-D agostic D

CH2R

Cp2Zr D H

H CH2R R H kD

CH2R D H R

D Cp2Zr D H

H CH2R H H2 R

H2 H H2DC CH2R D H R D

CH2R D CH2R H H H2DC R H2DC H H R syn (erythro) threo (anti)

H D H CH2R CH2R H2DC H H2DC R R H syn (erythro) threo (anti)

- Agostic H-interaction lowers T.S. energy relative to agostic-D

Group Exercise
[OpSc(H)(PMe3) H2 (4 atm) H 23 C Me >98% yield [OpSc(H)(PMe3) H2 (4 atm) D 23 C D

recent theoretical results favoring transition state B,9 we have adapted this catafytic hydrocyclization reaction along the lines of the Grubbs experiment to probe for a agostic assistance with the scandium system. trans,trans-l,6-d2-1,5-Hexadiene was employed as substrate, and as expected, OpSc(PMe3)H cleanly catalyzes its hydrocyclization to a mixture of cis- and transd2-methylcyclopentane(eq 2).1 2H{lH]NMR analysis reveals a ( I . I9 f 0.04): 1 ratio of transcis products at 25 OC (see supplementary material)."

Further support for agostic interactions from Bercaw

1

[OpSc(H)(PMe3) H2 (4 atm) 23 C

GROUP EXERCISE: 1. Provide a mechanism/stereochemical rationale that accounts for the observed KIE in the formation of d2-methylcyclopentane. 2. Provide a mechanistic rationale that explains why the selectivity is (8) Piers. W. E.;Shapiro, P. J.; Bunel, E. E.; Bercaw, J. E. Synlett 1990, opposite in the case of d2-methylcyclohexane. 14-84. (9) H. H. Brintzinger, private communication.
( I O ) In a typical procedure, a 10-15-mg sample of OpSc(PMe,)H was loaded into a 1 SO-mL thick-walled reactor equipped with a 4-mm Kontes needle valve. Toluene (4 mL) was added in vacuo, the scandium complex dissolved with warming, and ca. 100 equiv of rigorously dried trans,trans-

Assuming that an cy agostic interaction is, in fact, responsible,12 D the excess of trans-d2-methylcyclopentane may be rationalized as shown in Scheme I. Addition of achiral a,w-diene to achiral CH2D OpScH yields a precisely CH2D 5050 mixture of R and S 1,6-d2-5hexenyl-scandium complexes. Due to ring strain there should a (trans strong : preference for cis fusion of the pseudo 4,5 ring system 1.2 : 1 cis) in the transition state for olefin insertion.I3 As shown in Scheme I for the R isomer only, the face selection for insertion of the D D pendant olefin then depends on whether H or D occupies the a agostic position. The expected preference for H to occupy the CH excess CH2D bridging position'* leads to 2D of the R,R (trans) product. A similar analysis for the S enantiomer leads to the same conclusion: the trans isomer (in that case S,S) is produced in excess, if an 1.2 a :1 (cis : interaction trans) agostic assists olefin insertion into the Sc-C bond (see supplementary material for full analysis). Additional experiments support the supposition that the partitioning of stereochemistry is due to a kinetic deuterium isotope effect operating a t the CY methylene of the [OpScCHDCH2CH2CH,CH=CH D] intermediate: ( I ) the tramcis ratio varies in a normal enthalpic manner with tem-

the pendant olefin is not influenced by the geometry about its a 1 .OO f 0.05 ratio of trans:cis products, arguing against an a double bond; and (3) similarly, trans-l-dl-l,5-hexadiene gives agostic assisted insertion in their system, however. the same trans:cis ratio of 1.19 f 0.02 with the single deuteron The scandium hydride, {($-CSMe,),SiMe2JSc(PMe3)H partitioned equally (2H NMR) between methyl and ring positions ("OpSc( PMe,)H"), cleanly catalyzes the hydrocyclization of of the d,-methylcyclopentane product. 1,Shexadiene to methylcyclopentane.* In light of some very For longer chain diolefins, simple hydrogenation to a,w-d2recent theoretical results favoring transition state B,9 we have alkanes competes with hydrocyclization. Reaction of OpScadapted this catafytic hydrocyclization reaction along the lines (PMeJH with neat 1,Sheptadiene at -4 OC in the presence of of 1990, the Grubbs experiment to probe for a agostic assistance with m. Chem. SOC. I 1 2, 9406-9407 1 atm of H2 leads to an approximately 60:40 mixture of methe scandium system. trans,trans-l,6-d2-1,5-Hexadiene was emScheme I e-solvent hy-ployed thylcyclohexane and n-heptane. 1,7-Octadiene is converted exas substrate, and as expected, OpSc(PMe3)H cleanly eroatom lonecatalyzes its hydrocyclization to a mixture of cis- and transclusively to n-octane. Nonetheless, the partial hydrocyclization ects can often -D ' 0 of trans,trans-1,7-d2- 1,6-heptadiene allowed us to ascertain the d2-methylcyclopentane(eq 2).1 2H{lH]NMR analysis reveals ratio of trans- to cis-d2-methylcyclohexane products. We find a ( I . I9 f 0.04): 1 ratio of transcis products at 25 OC (see supOpScH art through aplementary material)." a (1.2 1 f 0.5):1 ratio of cis-d2-methylcyclohexane:frans-d2gratefully acmethylcyclohexane, although the analysis is less accurate due to o Longo. overlap of the cis-D resonance with that for the methyl deuterons in the 2H N M R spectrum (see supplementary material). This reversal of trans:cis ratio is entirely consistent with the expectation slightly slightly that face selectivity for pendant olefin approach would be opposite 1 ymerization favorev \sfavored to that for formation of the five-membered ring. The developing of six-membered ring adopts a chair-like conformation, and the n Q C-H pseudo bicyclic transition state is now trans fused. Thus, as illustrated below, preferential H in the a agostic position leads to the cis isomer.

Bercaw Solution

1.

cis-fused pseudo bicyclic T.S. is favored due to ring strain in the

2.

bel Beckman cal Synthesis f Technology Assuming that an cy agostic interaction is, in fact, responsible,12 may be rationalized fornia 91 125the excess of trans-d2-methylcyclopentane as shown in Scheme I. Addition of achiral a,w-diene to achiral gust I, 1990

OpScH yields a precisely 5050 mixture of R and S 1,6-d2-5olefin polym- hexenyl-scandium complexes. Due to ring strain there should y provide ana strong preference for cis fusion of the pseudo 4,5 ring system anism of this e-component in the transition state for olefin insertion.I3 As shown in Scheme isoelectronic,I for the R isomer only, the face selection for insertion of the or alkyls) and pendant olefin then depends on whether H or D occupies the a onsisting ofagostic position. The expected preference for H to occupy the metallocene bridging position'* leads to excess of the R,R (trans) product. A f the cyclo- OpSCH the S enantiomer leads to the same conclusion: - OpSCH or syndiospe-similar analysis for H2; H2; the trans isomer (in that case S,S) is produced in excess, if an oping that in ectron, do (ora agostic interaction assists olefin insertion into the Sc-C bond e or group 3 (see supplementary material for full analysis). ition metal), Additional experiments support the supposition that the parmetry of the titioning of stereochemistry is due to a kinetic deuterium isotope carbon bond effect operating a t the CY methylene of the ment of alkyl [OpScCH DCH2CH2CH,CH=CH D] intermediate: ( I ) the sumed in ra- tramcis ratio varies in a normal enthalpic manner with tem-

slightly favored

slightly disfavored

Our results provide good evidence for the modified GreenRooney pathway for chain propagation with these Ziegler-Natta systems.15 Moreover, they suggest a rationale for the apparent requirement that active catalysts be 14-electron alkyl derivatives with two vacant orbitals: one to acoommodate the incoming olefin, another for the a agostic interaction.I6

ation by these mative suited mechanism",

invokes CY C-H coordination to assist olefin insertion,6 a quite different transition-state geometry (B). (8) Piers. W. E.;Shapiro, P. J.; Bunel, E. E.; Bercaw, J. E. Synlett 1990,

discussions. We also thank Professor Hans Brintzinger for providing us with information prior to publication. This work was Bercaw, J. E., JACS, 1990 , 112,Sciences 9406 (Grant supported by the USDOE Office of Basic Energy No. DE-FG03-85ER113431), by Exxon Chemicals Americas, and by Shell Companies Foundation. W.E.P. thanks the National Sciences and Engineering Research Council of Canada and the Izaak Walton Killam Foundation for postdoctoral fellowship

The forming six-membered ring adopts a chair-like conformation in the pseudo bicyclic T.S., Acknowledgment. We thank Professors Bob Grubbs, Tom which trans-fused. Flood, Mauriceis Brookhart, and Dennis Dougherty for helpful

troscopic methods1t071currently used to characterize the 23.0 22 stereoregularity of poly(r-olefins). The 13C N M R signals of a polymer are most conveniently Fig. 4. 13C NMR spectra of isotactic polyprop 90% obtained with ror-MetSi(l-benz[e]indenyl related to its microstructure by a stereochemical notation develand ofatactic polypropene with random pentad oped by Bovey.'107"1 Relative configurations of neighboring isomer of the same catalyst (bottom). units (or "dyads") are designated as m (meso) for equally and r The tacticity and degree of stereo-regularity (rac'cmo) for unequally positioned substituents in a Fischer-type in PP stereoregular with [mmmm]> 0.95. projection of the polymer chain. In polypropene, the I3C N M R ! 13C is dependent on the configuation int(mmmm) shift of each CH, group is determined by the configurations of typical MAO-activated chiral an of it's four stereogenic neighbors [mmmm] = Chtral Metallocene Catalysts REVIEWS SUM[int(pentads)] two neighboring repeat units on either side;[108] each CH, sigyield polypropene with stereoregul 0.9.['063 ' I 3 ] At increased poly nal is thus to assignable to a particular "pentad" pattern, reprecould be expected m rbe retained r even m under catalysis conditions. > 0.95 is Highly isotactic 1 most of these homogeneous however, sented bywith the consecutive m oabove, r r [mmmm] designators framing the When activated Mfour A 0 in the manner described these Isotactic were indeed found, in independent studonstr-i~~etallocenesl' stereoselective[mmmm] than typical heterogen CH, group 04] under consideration (Scheme 9). All ten possible >90% ies by Ewen with (en)(thind),TiC12/MAO[1051 and by Kaminsky Similar eqn applies for syndiotactic r with = racemo (unequal) lysts." 14=1 and Kiilper ruc-(en)(thind),ZrClz/MA0,~1061 to polymerm = meso (equal) The 3C N M R signals associated w ize propene and other cr-olefins to give highly isotactic polymers. m m m m m m r r r r r r These findings led to extensive exploration of the mechanisms in the isotactic polymers produced by by which these catalysts control the stereochemistry of polymer .- JL$+.. -LLLL... cate that stereoregularity is controll growth and the effects of different metallocene structures on the tacticities and other properties of the polymers produced. metallocene catalyst and not by the as mmm r mm r m r m r T r T r m ed unit: Such "chain-end'' control w ...+.L,A-.. . . . 1 I 1 ,... . . . inversion pentad mmrm as a main e atactic 3.1. Catalyst Structures and Stereoselectivities sionally inverted chain-end configu r mm r r m r m m r r m Polypropene produced by MAO-activated chiral ansa-zirfollowed by units of the same configu conocenes such as rrrc-(en)(ind),ZrCI, or rac(en)(thind),ZrCl, control one would expect an err has similar isotacticity to polymers produced with heterogeneous Ziegler-Natta catalysts. For a more quantitative discusmmmr:mmrr :mmrm:mrrm = 1:0: 1 :O sion of these relations. we consider briefly the 13C N M R specmmmr :mmrr : distribution close to mm-centered mr-centered rr-centered troscopic methods1t071currently used to characterize the 23.0 22.0 21.0 20.0 19.0 observed these polymers (Schem Scheme 9. The ten possible stereochemical pentads of a polyolefin [107]. stereoregularity of poly(r-olefins). a for h H-H. Angew. Chem. Int.Fig. Ed. . 1995 , 34, The 13C N M R signals of aBrintzinger, polymer are most conveniently 4. Engl 13C NMR spectra of 1143 isotactic polypropene (CH, region) with [mmmnr] > lished for heterogeneous 90% obtained with ror-MetSi(l-benz[e]indenyl),ZrCl,iMAO [117 h. 120dl (top), related to its microstructure by a stereochemical notation develpentad distribution obtained withinsertion the f n m and ofatactic polypropene with random pected when olefin is ind oped by Bovey.'107"1 Relative configurations of neighboring

I " " I " " I " " I

Stereochemical Considerations

" 3 '

...bLLr_L...

JufT...

...%,...

I " " I " " I " " I ' " " ' ' " ~ ' ' "

isomer of the same catalyst (bottom).

1224 Chemical Reviews, 2000, Vol. 100, No. 4

Stereochemical Considerations

C oa t e s

Scheme 1. Chain-End and Enantiomorphic Site Mechanisms of Stereocontrol

Chain-End Control vs. Site Control

errors propagated

errors corrected
W. Chem. Rev. 2000, 100, 1223. cant, the mode of stereochemical regulation is referred are now available that can control Coates, the moG. lec ular to as polymer chain-end control. It should be noted weight, molecular weight distribution, comonomer Predicted 13C NMRand Patterns that in rare instances more than one stereogenic incorp orati on, and both the relative absolute center of the polymer can play a Distributions significant role in stereochemistry of a po lymer in a way that is often Chain-End Control Pentad Enantiomorphic Site Control Pentad Distributions stereoregulation. If the ligand set is chiral and impossible using conventional hetereogeneous cataoverrides the influence of the polymer chain end, the lysts. Although their commercial implementation in r cal m m r r m m m oc mhemi m m m mechanism m of stere direc tionmis termed the solution phase is often impractical, they can be enantiomorphic-site control (Scheme 1). In the heterogenized for efficient gas-phase or flow-through mmmr : mmrr : mmrm : mrrm = 2 : 2 : 0 : 1 mmmr : mmrra: stere mmrm : mrrm 1o :r0is :1 former mechanism, ochemi cal = err pr:o0 pareaction by attaching them to a solid support. Pergated, while in the latter a correction occurs since haps most importantly,( these defined molecularrr-triads) (r-dyads) the ligands direct the stereochemical events. based systems allow detailed structural and mechanistic studies. Thus, through theoretical and empirical Scheme 1 introduces the parameters that are used studies scientists can rapidly evolve new and imto describe the stereoselectivity of the monomer

Isotactic PP from Homogeneous Catalysts

Ewen studies with racemic and meso ansa-metallocenes
Zr-Cat-1:2 (86 mol, 56% rac, 44% meso) MAO 9.4 (mmol) (2.4 mol) Toluene, -60 C, 4 h n 6.0 g Polymer 63% isotactic (insoluble in pent.) n

37% atatic (soluble in pent.)

Ti-Cat-1

Ti-Cat-2

- 13C-NMR analysis of the triad fragments suggested a mixture of isotactic/atatic-PP - Author proposed that the isotactic fragment arose from the C2-symmetric cat-2 13C NMR of insoluble polymer C13 NMR of crude

Ewen, J. A. JACS, 1984, 106, 6355.

Later conrmed by Brintzinger using isomerically ansa-metallocene

Zr-Cat-3 (3.3 mol) MAO 5.6 (mmol) Toluene, 23 C, 0.5 h n 2.7 kg (mol >95% isotactic-PP Zr)-1 h-1
Zr-Cat-3

Brintzinger, H-H. Angew. Chem. Int. Ed. Engl. 1985, 24, 507

Ligand-Controlled PP-Synthesis
Observations of Ewen and Brintzinger led to further optimization of C2-Metallocene catalysts

metallocene 6 9 10 11 12 13 14 15 16 4th generatione

Tm productivityb (C)
188 5c 1.6d 190 99 403 245 875 47 20 132 149 162 137 145 146 150 161 160 162

Mw
24 000 4 000 134 000 36 000 195 000 330 000 213 000 920 000 400 000 900 000

[mmmm] 0.78 0.97 0.977 0.82 0.88 0.89 0.89 0.991 0.992 >0.99

Productivity: kg of PP/(mmol of Mh). 4th generation heterogeneous Z-N catalyst.

- Highly isotactic-PP can now be achieved with homogeneous C2 catalysts - Catalyst productivities and polymer properties are close to modern heterogeneous Z-N catalysts

Coates, G. W. Chem. Rev. 2000, 100, 1223.

-A question that arose was could syndiotactic polymers also be prepared

efins are the focus of intense current of metallocene catalysts from groups epared. The tacticity of polypropylene he structure of the metallocene cataR methylene group (P) and the methyl group of the propylene etallocenes generally afford atactic monomer to assume a trans relationship dominates, forcing the metric metallocenes produce highly 1300 Chemic al Rfluorenyl eviews, 2000ligand. , Vol. 100, The No. 4relatively methyl group down toward the C1 metallocenes also produce isotactic Initial studiesWhereas by Ewen flat with CS metallocenes led to syndiotactic-PP fluorenyl ligand with its open region between the benzo ly with less stereospecificity. Chart 18. Examples of Syndiospecific Cs-Symmetric substituents nicely accommodates this orientation. In contrast, metallocene catalysts are structurally 4 (1.3 mol)the ligand system for 2 lacks this feature. ctic polypropylene has been Zr-Catproduced MAO (10.7 wt%) A new ligand has been designed with 1,2-[SiMe2]2 linking ype of Cs symmetric ansa-metallocene 2 n 3,5-diisopropylcyclopentadienyl groups. of cyclopentadienyl and 25 C, 1 h nts thereof. According to the original (1.2 L) Zirconocene 4 (eq 1)7 thus incorporates all three features of 1: 26 g PP = 0.89, M =1.9 (a) Cs [rrrr] symmetry, (b) cyclopentadienyls of differing size, and w/Mn Zr-Cat-4 Ewen, O., JACS, 1988, 110, 6255. (c) steric bulk flanking the metallocene wedge with an open region have in center. Furthermore, this ligand design allows Similar ligand optimizations led to highly syndio-specic

Ligand Symmetry and PP-tacticity

catalysts Communications Communications to to the the Editor Editor

Razavi,2a

Zr-Cat-4a-d Communications to the Editor Table 1. Propylene Polymerizations Catalyst Derived from MAO with Table 1. Propylene Polymerizations with Catalyst Derived from a
Communications the Editor 4a-d and -ba to Polymerizations Table 1. 5a Propylene with Catalyst Derived from

the syndiospecificity arises ns occurring from alternating (enanetallocene wedge with the propylene way from the larger fluorenyl ligand. ng single-component, syndiospecific alysts led us to the ligand system of ocene 2,3 seemingly closely related to PP-tacticity is highly d that the bulky [SiMe ] substituents

4a-d and 5a-ba f 4a -d andcatalyst 5a-b 0C, Liq. C H6 entry activity [rrrr]g ]g [r]h [m]ii f g 3 [mmmm g h entry 1. catalyst [ rrrr ] [ mmmm ] [ r ] [m]i Table Propylene activity Polymerizations with Catalyst Derived from f g b a entry activity [rrrr ]g [mmmm [r]h [m ] 1 4a 2160 83.7 0.0 ] 94.0 6.0 4a d andcatalyst 5a b b 1 4ac 2160 83.7 0.0 94.0 6.0 b 2 4a 300 27.3 0.0 74.1 25.9 1 4ac 2160 f [rrrr 83.7 0.0 ]g 74.1 94.0 6.0 2 4a 300 27.3 0.0 25.9 entry catalyst activity ]g [mmmm [r]h [m ]i d c 3 4a 74200 76.0 0.1 92.6 7.4 2 4a 300 27.3 0.0 74.1 25.9 3 4ad 74200 76.0 0.1 92.6 7.4 b 4 4b 1750 98.9 0.0 99.6 0.4 1 4ad 2160 83.7 94.0 6.0 b 3 4a 74200 76.0 0.1 92.6 7.4 4 4bc 1750 98.9 0.0 99.6 0.4 b 5 4b 230 38.8 0.0 75.6 24.3 2 4a 300 27.3 74.1 25.9 c 4 4b 1750 98.9 0.0 99.6 0.4 5 4bb 230 38.8 0.0 75.6 24.3 d c 6 4c 1730 95.9 0.0 99.0 1.0 3 4a 74200 76.0 0.1 92.6 7.4 b 5 4b 230 38.8 0.0 75.6 24.3 6 4cc 1730 95.9 0.0 99.0 1.0 b b 7 4c 230 33.9 0.0 75.2 24.8 4 4b 1750 98.9 99.6 0.4 c 6 4c b 1730 95.9 0.0 99.0 24.8 1.0 7 4c 230 33.9 0.0 75.2 c 8 4d 722 90.5 0.0 96.9 3.1 5 4bcb 230 38.8 75.6 24.8 24.3 7 4c 230 33.9 0.0 75.2 8 4db 722 90.5 0.0 96.9 3.1 b 9 4d 200 29.6 0.0 76.2 6 4c c 1730 95.9 99.0 23.8 1.0 c 8 4d 722 90.5 0.0 96.9 3.1 9 4dc 200 29.6 0.0 76.2 23.8 b c 10 5ab 1500 83.1 0.0 94.4 5.6 7 4c 230 33.9 75.2 24.8 9 4d 200 29.6 0.0 76.2 23.8 Bercaw, J. E. JACS, 1996 , 118, 11988 10 5ac 1500 83.1 0.0 94.4 5.6 b b 11 5a 200 20.0 4.8 62.0 38.0 8 4d 722 90.5 0.0 96.9 3.1 10 5ac 1500 83.1 0.0 94.4 38.0 5.6 11 5a 200 20.0 4.8 62.0 b c c 12 5b 930 41.8 5.6 73.5 26.5 9 4d 200 29.6 0.0 76.2 23.8 b 11 5a c 200 20.0 4.8 62.0 26.5 38.0 12 5b 930 41.8 5.6 73.5 b 13 5b 156 0.0 61.2 14.6 10 5ab 1500 83.1 0.0 94.4 85.4 5.6 c 12 930 41.8 5.6 73.5 13 5bc 156 0.0 61.2 14.6 26.5 85.4 35b e c 14 5b 110 0.0 58.5 17.6 82.4 11 5a 200 20.0 4.8 62.0 38.0 e 13 5b 156 0.0 61.2 14.6 85.4 14 5bb 110 0.0 58.5 17.6 82.4 12 5b 930 41.8 5.6 73.5 26.5 14 5beS Information 110 0.0 58.5 17.6 b Liquid 82.4 a See Supporting for full experimental details. c a See Supporting 13 5b 156 0.0 61.2 details. 14.6 b Liquid 85.4 Information for full experimental a See Supporting propylene at 0 2 mg of for catalyst and 58.5 2000 equiv ofb Liquid MAO. e C; Information full experimental details. 14 5b 110 0.0 17.6 82.4 propylene at 0 C; 2 mg of catalyst and 2000 equiv of MAO. c Propyleneat (40 mL at 25 C; 10 mg of catalyst and c propylene 0 psig) C; din 2 35 mg oftoluene catalyst and 2000 equiv of MAO. Propylene (40 psig) in 35 mL toluene at 25 C; 10 mg of catalyst and a See b Liquid c Liquid propylene at 60 C; 300 equiv of MAO. 430 equiv of MAO. Supporting Information for full experimental details. Propylene (40 psig)din 35 mL toluene at 25 C; 10 mgequiv of catalyst and Liquid propylene at 60 C; 300 of MAO. 430 equiv of MAO. e Propylene (10 in toluene at 25 C; 10 mg of equiv catalyst and 430 propylene at 0 psig) C; d 2 mg of catalyst and 2000 of MAO. e Liquid propylene at 60 C; 300 equiv of 430 equiv of MAO. Propylene (10 psig) in toluene at 25 C; 10 mg of catalyst and 430 f Polymer isolated (g)/catalyst (g)/hour. g Percentage c e equiv of MAO. (40 in mL toluene at 25 C; 10 mg of gcatalyst and f Propylene (10 psig) psig) in35 toluene at 25 C; 10 mg of catalyst and 430

Scheme Scheme 1 1 Scheme 1 J. Am. Chem. Soc., Vol. 118, No. 47, 1996 11989

J. J. Am. Am. Chem. Chem. Soc., Soc., Vol. Vol. 118, 118, No. No. 47, 47, 1996 1996 11989 11989 J. Am. Chem. Soc., Vol. 118, No. 47, 1996 11989

n1 Scheme

Zr-Cat-4a-d

systematic variation of ligand the cyclopentadienyl dependent on the symmetrysubstituent (R) contained in the mirror plane, permitting steric changes for the C -> Syndiotactic C2 -> isotactic catalyst while maintaining C symmetry (e.g., 4a-d) or lowering
s

the overall symmetry to C1 (e.g., 5a,b). When activated with MAO, 4a-d and 5a,b are active

Unifying Stereochemical Models

C2 -> isotactic

- Polymer chain moves after each insertion (due to metallocyclobutane T.S.) - Coordination sites are homotopic - Same prochiral face of the olen is inserted, regardless of the coordination site

CS -> syndiotactic

- Coordination sites are enantiotopic - Opposite prochiral faces of the olen insert at each coordination site
Coates, G. W. Chem. Rev. 2000, 100, 1223.

Mechanisms of Racemization
Communications to the Editor
S Table 1. Propylene Polymerizations with Catalyst Derived from a 4a-d and 5a-b
entry 1 2 3 4 5 6 7 8 9 10 11 12 13 14
a

Site epimerization in C catalyst systems (chain swinging) Scheme 1

catalyst
f activity rrrr ]g [mmmm]g Zr-Cat [(2 mg)

J. Am. Chem. Soc., Vol. 118, No. 47, 1996 11989

[r]h

[m]i

MAO (2000 4ab 2160 83.7 eq.) 0.0 94.0 6.0 c 4a 300 27.3 0.0 74.1 25.9 Toluene/or liq. C3H6 , 4ad 74200 76.0 0.1 92.6 7.4 4bb 1750 0 C, 98.9 0.0 99.6 0.4 0.5 h c 4b 230 38.8 0.0 75.6 24.3 4cb 1730 95.9 0.0 99.0 1.0 4cc 230 33.9 0.0 75.2 24.8 4db 722 90.5 0.0 96.9 3.1 4dc 200 29.6 0.0 76.2 23.8 Experimental observation: 5ab 1500 83.1 0.0 94.4 5.6 c 200 20.0 4.8[rrrr]62.0 38.0 1.5a High propene pressure: = 41.8 5bb 930 41.8 5.6 73.5 26.5 (moderately 5bc 156 syndiotactic) 0.0 61.2 14.6 85.4 e 5b 110 0.0 58.5 17.6 = 82.4 2. Low propene pressure: [mmmm] 61.2

R = CHMeCMe3

(moderately isotactic) See Supporting Information for full experimental details. b Liquid propylene at 0 C; 2 mg of catalyst and 2000 equiv of MAO. c Propylene (40 psig) in 35 mL toluene at 25 C; 10 mg of catalyst and 430 equiv of MAO. d Liquid propylene at 60 C; 300 equiv of MAO. e Propylene (10 psig) in toluene at 25 C; 10 mg of catalyst and 430 f Polymer isolated (g)/catalyst (g)/hour. g Percentage equiv of -MAO. Author !s proposed that at low [propene] of [rrrr] or [mmmm] pentad by 13C NMR analysis. h [r] ) [rr] + is i [m] ) [swinging mm] + 0.5[mr ]. competitive with monomer 0.5[mr]. chain insertion (enchainment)
Zirconocene 4a produces polypropylene of syndiotacticity comparable to {(Et2C)(fluorenyl)(cyclopentadienyl)}ZrCl2.8 Zirconocene 4b3 exhibits the syndiospecificity: at11988 0C in Bercaw, J.highest E. et. al. JACS, 1996, 118, liquid propylene good yields of polypropylene are obtained having 98.9% rrrr. C1 zirconocene 5a performs similarly to Cs symmetric and closely related 4b. On the other hand, chiral 5b produces

The mechanisms for these processes are presently under further investigation.

Mechanisms for Racemization

Mechanisms of Chain Termination
1. Chain transfer to aluminum:

Chain-end epimerization

2. Beta-hydride transfer:

Resconi, L. et. al. Macromolecules, 1995, 28, 6667. Coates, G. W. Chem. Rev. 2000, 100, 1223.

Exploiting Site Epimerization

Catalysts for the synthesis of Hemisotactic-PP
Zr-Cat/MAO n

- Hemisotactic-PP contain isospecic monomer units separated by monomers of random stereochemistry

Mechanistic rationale

- Chiral ligand provides aspecic (random) and isospecic coordination sites

Coates, G. W. Chem. Rev. 2000, 100, 1223.

Ewens Symmetry Rules

-Number of well dened ligand are now available for the synthesis of PP-polymers with varying properties - Lead to the formulation of Ewen!s symmetry rules - What can synthetic chemists do with stereoselective homogeneous polymerization?
Resconi, L. et. al. Chem. Rev. 2000, 100, 1253.

Kinetic Resolutions of Olens

Basic idea
R kS fast R & R Chiral Z-N Catalyst kR slow R (enriched monomer) n R R (optically active polymer)

Where k = rate of monomer enchainment

First experiments were performed by Pino in 1963

TiCl4, Zn Me 2 Polymer Me Recovered monomer: [!]D = -0.75 Eantiopure authentic: [!]D = 36.0 Optically purity = 2%
Pino, P. et. al. JACS 1963, 85, 3888.

Me (2/1 ratio Zn/Ti, ~20 mol%) Me 20 C, 236 h

- Selectivities were very low - Proof of principle experiment - Little was known about the catalyst structure

Kinetic Resolutions with Zr-Metallocenes

Homogeneous Zr-catalysts (Bercaw)

- 13C-NMR analysis suggest Isostatic polymers were formed - Low but signicant values of s were observed for all olens - moderate to good s for 3,4dimethyl-1-pentene
Bercaw, J. E. et. al. JACS, 2004, 126, 8216.

Mechanistic and Stereochemical Rationale

- Authors propose a site epimerization to explain the formation of primarily isotactic polymer. - Enchainment of the (S)-enantiomer on the right side of the wedge is favored due to steric interactions

Structure Activity Relationships

-Author!s suggested that increasing steric bulk in the lower right quadrant could lead to higher selectivities - No further increases in selectivity observed - Chain-end control could be competing with catalyst
Bercaw, J. E. et. al. JACS, 2004, 126, 8216.

Chain-End Control vs. Site Control

Polymer contains two stereogenic centers
Zr-Cat/MAO ! " #' # $ n

-Side-chain and main chain chirality could be inuencing monomer enchainment

- How can site-control and chain end control be separated - Authors proposed a copolymerization with an achiral monomer
Scenario 1: site-control and chain-end control work in concert (s-homopoly > s-copoly) Scenario 2: site-control and chain-end control oppose each other (s-homopoly < s-copoly)
Bercaw, J. E. et. al. PNAS, 2006, 103, 15303.

Kinetic Resolution of Co-polymerization

R (S)-2 (1-2 mg), MAO (500/1) H2C CH2 (300 torr) Co-polymer Toluene/tetradecane, 25 C

-13CNMR and mp data were consistent with polymer structures containing few consecutive chiral repeat units - Data suggest that for all but one olen scenario 1 is operative (s-homopoly > s-copoly) - For 3-methyl-1-pentene site-control and chain-end control work uncooperatively

- Complex interactions of end-chain and site control make it difcult to rationally design new ligands

Conclusions
(1) Advent of homogeneous catalysts provided a more well-dened system for a mechanistic analysis of Z-N polymerization (1I) Variation of ligand symmetry in the metallocene allowed for the synthesis of a number of different polypropylene structures (III) Kinetic resolution of olens using homogeneous catalysts is very promising, but still in its infancy

Karl Ziegler-the last Al-Chemist ...because he turned aluminum into gold.

Excellent Reviews To Be Aware Of

I. Excellent reviews on stereochemistry and mechanism of Ziegler-Natta Polymerizations:
(1) Brintzinger, H-H.; Fischer, D.; Mulhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem. Int. Ed. Engl. 1995, 34, 1143-1170. (2) Coates, G. W. Chem. Rev. 2000, 100, 1223-1252. (3) Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F. Chem. Rev. 2000, 100, 1253-1346.

II. Review on co-catalysts and activators in Ziegler-Natta Polymerization:

Chen, E. Y-X.; Marks, T. J. Chem. Rev. 2000, 100, 1391-1434.

III. Reviews on agostic interactions in organometallic complexes:

(1) Brookhart, M.; Green, M. L. H.; Wong, L-L. Prog. Inorg. Chem. 1988, 36, 1-124 (2) Brookhart, M.; Green, M. L. H.; Parkin, G. Proc. Nat. Acad. Sci. 2007, 104, 6908-6914.

IV. Chemical Reviews volume 100, issue 4 is dedicated to metalcatalyzed polymerization

Backup: Evidence for MAO-Cluster