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Rare-Earth Metal Complexes Supported by Nitrogen-Containing Ligands in Olefin Polymerization

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Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes I

Part of the book series: Catalysis by Metal Complexes ((CMCO,volume 34))

Abstract

In this review the recent developments in the synthesis of rare-earth metal complexes active in catalysis of olefin polymerization are summarized. Alkyl (neutral and ate), cationic alkyl and hydrido complexes supported by nitrogen-containing ligands are considered. The polymerization-active complexes are classified according to monomer (ethylene, α-olefin, styrene), type of compound (neutral alkyl, cationic alkyl, ate-alkyl, hydrido) and the number of nitrogen atoms in supporting ligands. The properties of obtained polyolefins are discussed.

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References

  1. Watson PL, Parshall GW (1985) Organolanthanides in catalysis. Acc Chem Res 18:51–56

    Article  CAS  Google Scholar 

  2. Yasuda H (2000) Organo transition metal initiated living polymerizations. Prog Polym Sci 25:573–626

    Article  CAS  Google Scholar 

  3. Hou Z, Wakatsuki Y (2002) Recent developments in organolanthanide polymerization catalysts. Coord Chem Rev 231:1–22

    Article  CAS  Google Scholar 

  4. Yasuda H (2002) Organo-rare-earth-metal initiated living polymerization of polar and non-polar monomers. J Organomet Chem 647:128–138

    Article  CAS  Google Scholar 

  5. Gromada J, Carpentier J-F, Mortreux A (2004) Group 3 metalcatalysts for ethylene and α-olefin polymerization. Coord Chem Rev 248:397–410

    Article  CAS  Google Scholar 

  6. Evans WJ, Meadows JH, Hunter WE, Atwood JL (1984) Organolanthanide and organoyttrium hydride chemistry. 5. Improved synthesis of [(C5H4R)2YH(THF)]2 complexes and their reactivity with alkenes, alkynes, 1,2-propadiene, nitriles, and pyridine, including structural characterization of an alkylideneamido product. J Am Chem Soc 106:1291–1300

    Article  CAS  Google Scholar 

  7. Stern D, Sabat M, Marks TJ (1990) Manipulation of organolanthanide coordinative unsaturation. Synthesis, structures, structural dynamics, comparative reactivity, and comparative thermochemistry of dinuclear μ-hydrides and μ-alkyls with [μ-R2Si(Me4C5)(C5H4)]2 supporting ligation. J Am Chem Soc 112:9558–9575

    Article  CAS  Google Scholar 

  8. Shapiro PJ, Cotter WD, Schaefer WP, Labinger JA, Bercaw JE (1994) Model Ziegler-Natta α-olefin polymerization catalysts derived from[{(η5-C5Me4)SiMe2(η1-NCMe3)}(PMe3)Sc(μ2-H)]2 and[{(η5-C5Me4)SiMe2(η1-NCMe3)}Sc(μ2-CH2CH2CH3)]2. Synthesis, structures, and kinetic and equilibrium investigations of the catalytically active species in solution. J Am Chem Soc 116:4623–4640

    Article  CAS  Google Scholar 

  9. Hulzsch KC, Voth V, Beckerle K, Spaniol TP, Okuda J (2000) Single-component polymerization catalysts for ethylene and styrene: synthesis, characterization, and reactivity of alkyl and hydrido yttrium complexes containing a linked amido—cyclopentadienyl ligand. Organometallics 19:228–243

    Article  Google Scholar 

  10. Trifonov AA, Spaniol TP, Okuda J (2001) Yttrium hydrido complexes that contain a less “constrained geometry” ligand: synthesis, structure, and efficient hydrosilylation catalysis. Organometallics 20:4869–4874

    Article  CAS  Google Scholar 

  11. Casey CP, Tunge JA, Lee T-Y, Carpenetti DW (2002) Kinetics and mechanism of formation of yttrium alkyl complexes from (Cp*2YH)2 and alkenes. Organometallics 21:389–396

    Article  CAS  Google Scholar 

  12. Casey CP, Tunge JA, Lee TY, Fagan MA (2003) Structural dependence of thermodynamics of alkene binding to yttrium alkyl complexes and of kinetics of alkyl migration to coordinated alkenes. J Am Chem Soc 125:2641–2651

    Article  CAS  Google Scholar 

  13. Trifonov AA, Spaniol TP, Okuda J (2004) Hydrosilylation of dienes by yttrium hydrido complexes containing a linked amido-cyclopentadienyl ligand. Dalton Trans 2245–2250

    Google Scholar 

  14. Luo Y, Hou Z (2007) Computational study of ethylene insertion into the metal—hydrogen bond of the tetranuclear yttrium polyhydrido complex [(η5–C5Me4SiMe3)YH2]4. Organometallics 26:2941–2944

    Article  CAS  Google Scholar 

  15. Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A 32:751–767

    Article  Google Scholar 

  16. Gibson VC, Spitzmesser SK (2003) Advances in non-metallocene olefin polymerization catalysis. Chem Rev 103:283–316

    Article  CAS  Google Scholar 

  17. Edelmann FT, Freckmann DMM, Schumann H (2002) Synthesis and structural chemistry of non-cyclopentadienyl organolanthanide complexes. Chem Rev 102:1851–1896

    Article  CAS  Google Scholar 

  18. Piers WE, Emslie DJH (2002) Non-cyclopentadienyl ancillaries in organogroup 3 metal chemistry: a fine balance in ligand design. Coord Chem Rev 131:233–255

    Google Scholar 

  19. Trifonov AA (2007) Non-metallocene rare-earth organometallic derivatives: synthesis, structure and application in the catalysis of transformations of unsaturated substrates. Russ Chem Rev 76:1051–1072

    Article  CAS  Google Scholar 

  20. Green MLH (1995) A new approach to the formal classification of covalent compounds of the elements. J Organomet Chem 500:127–148

    Article  CAS  Google Scholar 

  21. Parkin G (2007) Classification of organotransition metal compounds. In: Crabtree RH, Mingos MD (eds) Comprehensive organometallic chemistry 3rd edn vol. 1. Elsevier, Amsterdam

    Google Scholar 

  22. Morss LR (1976) Thermochemical properties of yttrium, lanthanum, and the lanthanide elements and ions. Chem Rev 76:827–841

    Article  CAS  Google Scholar 

  23. Schumann H, Meese-Marktscheffel JA, Esser L (1995) Synthesis, structure, and reactivity of organometallic π-complexes of the rare earths in the oxidation state Ln3+ with aromatic ligands. Chem Rev 95:865–986

    Article  CAS  Google Scholar 

  24. Arndt S, Okuda J (2002) Mono(cyclopentadienyl) complexes of the rare-earth metals. Chem Rev 102:1953–1976

    Article  CAS  Google Scholar 

  25. Okuda J (2003) Rare earth metal complexes that contain linked amido-cyclopentadienyl ligands: ansa-metallocene mimics and “constrained geometry” catalysts. Dalton Trans 2367–2378

    Google Scholar 

  26. Long DP, Bianconi PA (1996) A catalytic system for ethylene polymerization based on group III and lanthanide complexes of tris(pyrazolyl)borate ligands. J Am Chem Soc 118:12453–12454

    Article  CAS  Google Scholar 

  27. Fryzuk MD, Giesbrecht G, Rettig SJ (1996) Synthesis and characterization of the five-coordinate scandium dialkyl complexes ScR2[N(SiMe2CH2PPri 2)2] (R = Me, Et, CH2SiMe3). Organometallics 15:3329–3336

    Article  CAS  Google Scholar 

  28. Arndt S, Okuda J (2005) Cationic alkyl complexes of rare-earth metals: synthesis, structure, and reactivity. Adv Synth Catal 347:339–354

    Article  CAS  Google Scholar 

  29. Zeimentz PM, Arndt S, Elvidge BR, Okuda J (2006) Cationic organometallic complexes of scandium, yttrium, and the lanthanoids. Chem Rev 106:2404–2433

    Article  CAS  Google Scholar 

  30. Hou Z, Luo Y, Li X (2006) Cationic rare earth metal alkyls as novel catalysts for olefin polymerization and copolymerization. J Organomet Chem 691:3114–3121

    Article  CAS  Google Scholar 

  31. Bambirra S, Bouwkamp MW, Meetsma A, Hessen B (2004) One ligand fits all: cationic mono(amidinate) alkyl catalysts over the full size range of the group 3 and lanthanide metals. J Am Chem Soc 126:9182–9183

    Article  CAS  Google Scholar 

  32. Bambirra S, Van Leusen D, Meetsma A, Hessen B, Teuben JH (2003) Yttrium alkyl complexes with a sterically demanding benzamidinate ligand: synthesis, structure and catalytic ethane polymerization. Chem Commun 522–523

    Google Scholar 

  33. Bambirra S, Meetsma A, Hessen B (2006) Lanthanum tribenzyl complexes as convenient starting materials for organolanthanum chemistry. Organometallics 25:3454–3462

    Article  CAS  Google Scholar 

  34. Hayes PG, Piers WE (2002) Cationic scandium methyl complexes supported by a β-diketiminato (“nacnac”) ligand framework. J Am Chem Soc 124:2132–2133

    Article  CAS  Google Scholar 

  35. Kretschmer WP, Meetsma A, Hessen B, Schmalz T, Qayyum S, Kempe R (2006) Reversible chain transfer between organoyttrium cations and aluminium: synthesis of aluminium-terminated polyethylene with extremely narrow molecular-weight distribution. Chem Eur J 12:8969–8978

    Article  CAS  Google Scholar 

  36. Kempe R (2007) Coordinative chain transfer polymerization (CCTP). Chem Eur J 13:2764–2773

    Article  CAS  Google Scholar 

  37. Döring C, Kretschmer WP, Kempe R (2010) Aminopyridinate-stabilized lanthanoid complexes: synthesis, structure and polymerization of ethylene and isoprene. Eur J Inorg Chem 2853–2860

    Google Scholar 

  38. Zimmermann M, Törnroos KW, Waymouth RM, Anwander R (2008) Structure—reactivity relationships of amido-pyridine-supported rare-earth-metal alkyl complexes. Organometallics 27:4310–4317

    Article  CAS  Google Scholar 

  39. Lawrence SC, Ward BD, Dubberley SR, Kozak CM, Mountford P (2003) Chem Commun 2880–2881

    Google Scholar 

  40. Ge S, Meetsma A, Hessen B (2007) Monoanionic fac-κ3 ligands derived from 6-amino-1, 4-diazepine: ligand dependence of stability and catalytic activity of their scandium alkyl derivatives. Organometallics 26:5278–5284

    Article  CAS  Google Scholar 

  41. Bambirra S, Van Leusen D, Meetsma A, Hessen B, Teuben JH (2001) Neutral and cationic yttrium alkyl complexes with linked 1, 4, 7-triazacyclononane-amide monoanionic ancillary ligands: synthesis and catalytic ethene polymerization. Chem Comm 637–638

    Google Scholar 

  42. Bambirra S, Van Leusen D, Tazelaar CGJ, Meetsma A, Hessen B (2007) Rare earth metal alkyl complexes with methyl-substituted triazacyclononane-amide ligands: ligand variation and ethylene polymerization catalysis. Organometallics 26:1014–1023

    Article  CAS  Google Scholar 

  43. Bambirra S, Boot SJ, Van Leusen D, Meetsma A, Hessen B (2004) Yttrium alkyl complexes with triamino—amide ligands. Organometallics 23:1891–1898

    Article  CAS  Google Scholar 

  44. Howe RG, Tredget CS, Lawrence SC, Subongkoj S, Cowley AR, Mountford P (2006) A novel transformation of a zirconium imido compound and the development of a new class of N3 donor heteroscorpionate Ligand. Chem Commun 223–225

    Google Scholar 

  45. Marinescu SC, Agapie T, Day MW, Bercaw JE (2007) Group 3 dialkyl complexes with tetradentate (L, L, N, O; L = N, O, S) monoanionic ligands: synthesis and reactivity. Organometallics 26:1178–1190

    Article  CAS  Google Scholar 

  46. Ephritikhine M (1997) Synthesis, structure, and reactions of hydride, borohydride, and aluminohydride compounds of the f-elements. Chem Rev 97:2193–2242

    Article  CAS  Google Scholar 

  47. Jeske G, Lauke H, Mauermann H, Schumann H, Marks TJ (1985) Highly reactive organolanthanides. A mechanistic study of catalytic olefin hydrogenation by bis(pentamethylcyclopentadienyl) and related 4f complexes. J Am Chem Soc 107:8111–8118

    Article  CAS  Google Scholar 

  48. Conticello VP, Brard L, Giardello MA, Tsyji Y, Sabat M, Stern CL, Marks TJ (1992) Chiral organolanthanide complexes for enantioselective olefin hydrogenation. J Am Chem Soc 114:2761–2762

    Article  CAS  Google Scholar 

  49. Jeske G, Lauke H, Mauermann H, Swepston PN, Schumann H, Marks TJ (1985) Highly reactive organolanthanides. Systematic routes to and olefin chemistry of early and late bis(pentamethylcyclopentadienyl) 4f hydrocarbyl and hydride complexes. J Am Chem Soc 107:8091–8103

    Article  CAS  Google Scholar 

  50. Mauermann H, Swepston PN, Marks TJ (1985) The 5f3 vs. 4f3. Routes to and properties of highly reactive neodymium(III) hydrocarbyl and hydride complexes. Organometallics 4:200–2002

    Article  CAS  Google Scholar 

  51. Jeske G, Schock LE, Swepston PN, Schumann H, Marks TJ (1985) Highly reactive organolanthanides. Synthesis, chemistry, and structures of 4f hydrocarbyls and hydrides with chelating bis(polymethylcyclopentadienyl) ligands. J Am Chem Soc 107:8103–8110

    Article  CAS  Google Scholar 

  52. Desurmont G, Li Y, Yasuda H, Maruo T, Kanehisha N, Kai Y (2000) Reaction pathway for the formation of binuclear samarocene hydride from monomeric alkyl samarocene derivative and the effective catalysis of samarocene hydride for the block copolymerization of ethylene with polar monomers. Organometallics 19:1811–1813

    Article  CAS  Google Scholar 

  53. Molander GA, Romero JAC (2002) Lanthanocene catalysts in selective organic synthesis. Chem Rev 102:2161–2186

    Article  CAS  Google Scholar 

  54. Harrison KN, Marks TJ (1992) Organolanthanide-catalyzed hydroboration of olefins. J Am Chem Soc 114:9220–9221

    Article  CAS  Google Scholar 

  55. Bijpost EA, Duchateau R, Teuben JH (1995) J Mol Catal 95:121

    Article  CAS  Google Scholar 

  56. Konkol M, Okuda J (2008) Non-metallocene hydride complexes of rare-earth metals. Coord Chem Rev 252:1577–1591

    Article  CAS  Google Scholar 

  57. Duchateau R, van Wee CT, Meetsma A, van Duijnen PT, Teuben JH (1996) Ancillary ligand effects in organoyttrium chemistry: synthesis, characterization, and electronic structure of bis(benzamidinato)yttrium compounds. Organometallics 15:2279–2290

    Article  CAS  Google Scholar 

  58. Duchateau R, van Wee CT, Teuben JH (1996) Insertion and C − H bond activation of unsaturated substrates by bis(benzamidinato)yttrium alkyl, [PhC(NSiMe3)2]2YR (R = CH2Ph·THF, CH(SiMe3)2), and hydrido, {[PhC(NSiMe3)2]2Y(μ-H)}2, compounds. Organometallics 15:2291–2302

    Article  CAS  Google Scholar 

  59. Hagadorn JR, Arnold J (1996) Preparation of scandium complexes with benzamidinate ligands: synthesis and reactivity of alkyl and hydrido derivatives. Organometallics 15:984–991

    Article  CAS  Google Scholar 

  60. Trifonov AA, Fedorova EA, Fukin GK, Bochkarev MN (2004) Post-metallocene hydridolanthanide chemistry: [{Lu{(Me3Si)2NC(Ni-Pr)2}2(μ-H)}]—a novel lanthanide hydride in a non-cyclopentadienyl coordination environment; synthesis, structure and catalytic activity in olefin polymerization. Eur J Inorg Chem 4396–4401

    Google Scholar 

  61. Trifonov AA, Skvortsov GG, Lyubov DM, Skorodumova NA, Fukin GK, Baranov EV, Glushakova VN (2006) Post-metallocene lanthanide-hydrido chemistry: a new family of complexes [{Ln{(Me3Si)2NC(Ni-Pr)2}2(μ-H)}2]. Chem Eur J 12:5320–5327

    Article  CAS  Google Scholar 

  62. Lyubov DM, Bubnov AM, Fukin GK, Dolgushin FM, Yu Antipin M, Pelcé O, Schappacher M, Guillaume SM, Trifonov AA (2008) Hydrido complexes of yttrium and lutetium supported by bulky guanidinato ligands [{Ln(μ-H){(Me3Si)2NC(Ni-Pr)2}2}2]. Eur J Inorg Chem 2090–2098

    Google Scholar 

  63. Gountchev TI, Don Tilley T (1999) Yttrium complexes of the chelating, C 2-Symmetric, bis(silylamido)biphenyl ligand [DADMB]2− (= {[6,6’-Me2-(C6H3)2](2,2’-NSiMe2 tBu)2}2−). Organometallics 18:2896–2905

    Article  CAS  Google Scholar 

  64. Lyubov DM, Döring C, Fukin GK, Cherkasov AV, Shavyrin AS, Kempe R, Trifonov AA (2008) Selective assembly of trinuclear rare-earth alkyl hydrido clusters supported by amidopyridinate ligands. Organometallics 27:2905–2907

    Article  CAS  Google Scholar 

  65. Lyubov DM, Fukin GK, Cherkasov AV, Shavyrin AS, Trifonov AA, Luconi L, Bianchini C, Meli A, Giambastiani G (2009) Selective σ-bond metathesis in alkyl–Aryl and alkyl–benzyl yttrium complexes. New aryl–and benzyl–hydrido yttrium derivatives supported byamidopyridinate ligands. Organometallics 28:1227–1232

    Article  CAS  Google Scholar 

  66. Luconi L, Lyubov DM, Bianchini C, Rossin A, Faggi C, Fukin GK, Cherkasov AV, Shavyrin AV, Trifonov AA, Giambastiani G (2010) Yttrium-amidopyridinate complexes: synthesis and characterization of yttrium-alkyl and yttrium-hydrido derivatives. Eur J Inorg Chem 608–620

    Google Scholar 

  67. Luo Y, Nishiura M, Hou Z (2007) Rare earth metal bis(alkyl) complexes bearing a monodentate arylamido ancillary ligand: Synthesis, structure, and Olefin polymerization catalysis. J Organomet Chem 692:536–544

    Article  CAS  Google Scholar 

  68. Hajela S, Schaefer WP, Bercaw JE (1997) Highly electron deficient group 3 organometallic complexes based on the 1, 4, 7-trimethyl-1, 4, 7-triazacyclononane ligand system. J Organomet Chem 532:45–53

    Article  CAS  Google Scholar 

  69. Ward BD, Bellemin-Laponnaz S, Gade LH (2005) C3 chirality in polymerization catalysis: a highly active dicationic scandium(III) catalyst for the isoselective polymerization of 1-hexene. Angew Chem Int Ed 44:1668–1671

    Article  CAS  Google Scholar 

  70. Lukešová L, Ward BD, Bellemin-Lapoonaz S, Wadepohl H, Gade LH (2007) High activity control in organolanthanide polymerization catalysis: formation of isotactic poly(α-oalkenes) with chiral C 3-symmetric thullium complex. Dalton Trans 920–922

    Google Scholar 

  71. Lukešová L, Ward BD, Bellemin-Lapoonaz S, Wadepohl H, Gade LH (2007) C3-Symmetric chiral organolanthanide complexes: synthesis, characterization, and stereospecific polymerization of α-olefins. Organometallics 26:4652–4657

    Article  Google Scholar 

  72. Fang X, Li X, Hou Z, Assoud J, Zhao R (2009) 1, 2-Azaborolyl-ligated half-sandwich complexes of scandium(III) and lutetium(III): synthesis, structures, and syndiotactic polymerization of styrene. Organometallics 28:517–522

    Article  CAS  Google Scholar 

  73. Liu D, Luo Y, Gao W, Cui D (2010) Stereoselective polymerization of styrene with cationic scandium precursors bearing quinolyl aniline ligands. Organometallics 29:1916–1923

    Article  CAS  Google Scholar 

  74. Luo Y, Yao Y, Shen Q (2002) [(Me3Si)2NC(Ni-Pr)2]2Ln(μ-Me)2Li(TMEDA) (Ln = Nd, Yb) as effective single-component initiators for styrene polymerization. Macromolecules 35:8670–8671

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, GSP-445, 603950, Nizhny Novgorod, Russia

    Alexander A. Trifonov

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  1. Alexander A. Trifonov
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Editors and Affiliations

  1. CSIC-Universidad de Sevilla, Instituto de Investigaciones Químicas, C/ Americo Vespucio, 49, Sevilla, 41092, Spain

    Juan Campora

  2. Institute of Chemistry of OrganoMetallic, National Council of Research - CNR, Via Madonna del Piano 10, Florence, 50019, Italy

    Giuliano Giambastiani

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Trifonov, A.A. (2011). Rare-Earth Metal Complexes Supported by Nitrogen-Containing Ligands in Olefin Polymerization. In: Campora, J., Giambastiani, G. (eds) Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes I. Catalysis by Metal Complexes, vol 34. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-3815-9_3

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