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Topics in Catalysis

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01-08-2013 | Original Paper

On the Origin of Living Polymerization over o-Fluorinated Post-titanocene Catalysts

Authors: Evgenii P. Talsi, Konstantin P. Bryliakov

Published in: Topics in Catalysis | Issue 11/2013

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Abstract

Group 4 bis(phenoxyimine) and related complexes are highly active olefin polymerization catalysts of the post-metallocene family. When activated with methylalumoxane, titanium complexes bearing o-fluoroaryl substituents can conduct living polymerization of ethylene and propylene. In spite of more than 10-year history of such catalysts, the origin of living behavior of such catalysts remains open to questions. This work presents the state of the art of the discussion on the living nature of single-site post-metallocene titanium based catalysts bearing o-fluoroaryl substituents. Recent experimental and theoretical results are discussed.

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“Through-space” contribution to the observed C,F coupling could not a priori be ruled out.

Note that each molecule had one ¹²CH₃– end group originating from ¹²C–MAO. The other end group of polymers in Table 2 was either H ₃ ¹³ C–¹³CH₂–, or H ₃ ¹² C–¹³CH₂–, or H ₂ ¹³ C=.

The characteristic ¹³C NMR pattern of terminal vinyl groups {δ 114 (H₂ C=CH–CH₂–), 139 (H₂C=CH–CH₂–), 34 (H₂C=CH–CH₂–)} was not observed in either the living or non-living catalyst systems.

Terminal vinylidene groups (toluene-d₈, 25 °C), ¹³C, δ: 109.0 (H ₂ ¹³ C=¹³C(¹²CH₃)–¹³CH₂–), 36.6 (H ₂ ¹³ C=¹³C(¹²CH₃)–¹³ CH₂–), 28.2 (H ₂ ¹³ C=¹³C(¹²CH₃)–¹³CH₂–¹³ CH₂–). The=C(CH₃)– carbon (expected δ 22) was not detected by ¹³C NMR because it originated from non-labeled ¹²C-AlMe₃. The=C(CH₃)– carbon (expected δ 145-146) was not reliably observed due to (1) the absence of NOE signal enhancement and (2) due to splitting into a doublet of doublets by the interaction with two adjacent ¹³C carbon atoms. We note that terminal vinylidene groups were erroneously marked as terminal vinyl groups in Figure 5 of Ref. [41].

Webster OW (1991) Science 251:887CrossRef

Szwarc M (1998) J Polym Sci Polym Chem 36:IX

Gibson VC, Spitzmesser SK (2003) Chem Rev 103:283CrossRef

Coates GW, Hustad PD, Reinartz S (2002) Angew Chem Int Ed 41:2236CrossRef

Makio H, Kashiwa N, Fujita T (2002) Adv Synth Catal 344:477CrossRef

Mitani M, Saito J, Ishii SI, Nakayama Y, Makio H, Matsukawa, Matsui S, Mohri JI, Furuyama R, Terao H, Bando H, Tanaka H, Fujita T (2004) Chem Rec 4:137

Furuyama R, Saito J, Ishii S, Makio H, Mitani M, Tanaka H, Fujita T (2005) J Organomet Chem 690:4398CrossRef

Domski GJ, Rose JM, Coates GW, Bolig AD, Brookhart M (2007) Progr Polym Sci 32:30CrossRef

Makio H, Fujita T (2009) Acc Chem Res 42:1532CrossRef

10.

Makio H, Terao H, Iwashita A, Fujita T (2011) Chem Rev 111:2363CrossRef

11.

Tian J, Hustad PD, Coates GW (2001) J Am Chem Soc 123:5134CrossRef

12.

Saito J, Mitani M, Mohri J, Yoshida Y, Matsui S, Ishii S, Kojoh S, Kashiwa N, Fujita T (2001) Angew Chem Int Ed 40:2918CrossRef

13.

Mitani M, Mohri J, Yoshida Y, Saito J, Ishii S, Tsuru K, Matsui S, Furuyama R, Nakano T, Tanaka H, Kojoh S, Matsugi T, Kashiwa N, Fujita T (2002) J Am Chem Soc 124:3327CrossRef

14.

Mitani M, Nakano T, Fujita T (2003) Chem Eur J 9:2397CrossRef

15.

Kui SCF, Zhu N, Chan MCW (2003) Angew Chem Int Ed 42:1628CrossRef

16.

Chan MCW, Kui SCF, Cole JM, McIntyre GJ, Matsui S, Zhu N, Tam KH (2006) Chem Eur J 12:2607CrossRef

17.

Chan MCW (2008) Chem Asian J 3:18CrossRef

18.

So LC, Liu CC, Chan MCW, Lo JCY, Sze KH, Zhu N (2012) Chem Eur J 18:565CrossRef

19.

Memmler H, Walsh K, Gade LH, Lauher JW (1995) Inorg Chem 34:4062CrossRef

20.

Findeis B, Schubart M, Gade LH, Möller F, Scowen I, McPartlin M (1996) J Chem Soc Dalton Trans 125

21.

Karl J, Erker G, Fröhlich R (1997) J Am Chem Soc 119:11165CrossRef

22.

Schrock RR, Adamchuk J, Ruhland K, Lopez LPH (2003) Organometallics 22:5079CrossRef

23.

Ritter T, Day MW, Grubbs RH (2006) J Am Chem Soc 128:11768CrossRef

24.

Popeney CS, Rheingold AL, Guan Z (2009) Organometallics 28:4452CrossRef

25.

Hilton J, Sutcliffe LH (1975) Progr NMR Spectrosc 10:27CrossRef

26.

Gribble GW, Olson ER, Brown JH, Bushweller CH (1993) J Org Chem 58:1631CrossRef

27.

Mele A, Salani G, Viani F, Bravo P (1997) Magn Reson Chem 35:168CrossRef

28.

Noveski D, Braun T, Neumann B, Stammler A, Stammler HG (2004) Dalton Trans 4106

29.

Pogodin S, Rae ID, Agranat I (2006) Eur J Org Chem 5059

30.

Xie X, Yuan Y, Krüger R, Bröring M (2009) Magn Reson Chem 47:1024CrossRef

31.

Talarico G, Busico V, Cavallo L (2004) Organometallics 23:5989CrossRef

32.

Furuyama R, Saito J, Ishii S, Mitani M, Matsui S, Tohi Y, Makio H, Matsukawa N, Tanaka H, Fujita T (2003) J Mol Catal A Chem 200:31CrossRef

33.

Pärssinen A, Luhtanen T, Klinga M, Pakkanen T, Leskelä M, Repo T (2005) Eur J Inorg Chem 2100

34.

Villani V, Giammarino G (2011) Macromol Theory Simul 20:174CrossRef

35.

Makio H, Fujita T (2004) Macromol Symp 213:221CrossRef

36.

Makio H, Oshiki T, Takai K, Fujita T (2005) Chem Lett 34:1382CrossRef

37.

Bryliakov KP, Kravtsov EA, Pennington DA, Lancaster SJ, Bochmann M, Brintzinger H, Talsi EP (2005) Organometallics 24:5660CrossRef

38.

Bryliakov KP, Kravtsov EA, Broomfield L, Talsi EP, Bochmann M (2007) Organometallics 26:288CrossRef

39.

Yu SM, Mecking S (2008) J Am Chem Soc 130:13204CrossRef

40.

Bryliakov KP, Talsi EP, Möller HM, Baier MC, Mecking S (2010) Organometallics 29:4428CrossRef

41.

Möller HM, Baier MC, Mecking S, Talsi EP, Bryliakov KP (2012) Chem Eur J 18:848CrossRef

42.

Britovsek GJP, Cohen SA, Gibson VC, van Meurs M (2004) J Am Chem Soc 126:10701CrossRef

43.

Białek M (2010) J Polym Sci A Polym Chem 48:3209CrossRef

Title: On the Origin of Living Polymerization over o-Fluorinated Post-titanocene Catalysts
Authors: Evgenii P. Talsi
Konstantin P. Bryliakov
Publication date: 01-08-2013
Publisher: Springer US
Published in: Topics in Catalysis / Issue 11/2013
Print ISSN: 1022-5528
Electronic ISSN: 1572-9028
DOI: https://doi.org/10.1007/s11244-013-0055-9

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