Cationic Tropidinyl Scandium Catalyst: A Perfectly Acceptable Substitute for Cationic Half-Sandwich Scandium Catalysts in cis-1,4-Polymerization of Isoprene and Copolymerization with Norbornene

Different nonmetallocene rare earth metal alkyl complexes such as monotropidinyl (Trop) scandium dialkyl complex (Trop)Sc(CH2SiMe3)2(THF) (1), ditropidinyl yttrium alkyl complex (Trop)2Y(CH2SiMe3)(THF) (3) as well as binuclear lutetium alkyl complex bearing one tetradentate dianionic 6-N-methyl-1,4-cycloheptadienyl (NMCH) ligand [(NMCH)Lu(CH2SiMe3)(THF)]2 (2) have been synthesized in high yields via one-pot acid–base reaction by using of the tris(trimethylsilylmethyl) rare earth metal complexes with the readily available natural product tropidine. The polymerization experiments indicate that the monotropidinyl scandium dialkyl complex 1 displays reactivity akin to that of the analogous monocyclopentadienyl scandium dialkyl complexes. In the presence of activator and a small amount of AlMe3, complex 1 exhibits similar activities (up to 1.6 × 106 g molSc–1 h–1) but higher cis-1,4-selectivities (up to 100%) than (C5H5)Sc(CH2SiMe3)2(THF) (cis-1,4-selectivity as 95%) in the isoprene polymerization, yielding th...

[1]  Shuang Yao,et al.  Syntheses, Structure, and Properties of Mixed Cp-Amidinate Rare-Earth-Metal(III) Complexes , 2014 .

[2]  Shihui Li,et al.  Binuclear Rare-Earth-Metal Alkyl Complexes Ligated by Phenylene-Bridged β-Diketiminate Ligands: Synthesis, Characterization, and Catalysis toward Isoprene Polymerization , 2013 .

[3]  Gaixia Du,et al.  Quasi-Living trans-1,4-Polymerization of Isoprene by Cationic Rare Earth Metal Alkyl Species Bearing a Chiral (S,S)-Bis(oxazolinylphenyl)amido Ligand , 2013 .

[4]  Kun Jin,et al.  Bis(oxazolinyl)phenyl-ligated rare-earth-metal complexes: highly regioselective catalysts for cis-1,4-polymerization of isoprene. , 2013, Inorganic chemistry.

[5]  Xiaoying Wang,et al.  Aluminum Effects in the Syndiospecific Copolymerization of Styrene with Ethylene by Cationic Fluorenyl Scandium Alkyl Catalysts , 2013 .

[6]  Dongmei Cui,et al.  Ligands Dominate Highly Syndioselective Polymerization of Styrene by Using Constrained-geometry-configuration Rare-earth Metal Precursors , 2012 .

[7]  H. Koshino,et al.  Scandium-Catalyzed Cyclocopolymerization of 1,5-Hexadiene with Styrene and Ethylene: Efficient Synthesis of Cyclopolyolefins Containing Syndiotactic Styrene–Styrene Sequences and Methylene-1,3-cyclopentane Units , 2011 .

[8]  H. Koshino,et al.  Cycloterpolymerization of 1,6-Heptadiene with Ethylene and Styrene Catalyzed by a THF-Free Half-Sandwich Scandium Complex , 2011 .

[9]  T. Marks,et al.  Multinuclear olefin polymerization catalysts. , 2011, Chemical reviews.

[10]  Z. Hou,et al.  Highly Cis-1,4-Selective Living Polymerization of 1,3-Conjugated Dienes and Copolymerization with ε-Caprolactone by Bis(phosphino)carbazolide Rare-Earth-Metal Complexes , 2011 .

[11]  H. Terao,et al.  FI catalysts for olefin polymerization--a comprehensive treatment. , 2011, Chemical reviews.

[12]  Xiao Liu,et al.  Living 3,4-Polymerization of Isoprene by Cationic Rare Earth Metal Alkyl Complexes Bearing Iminoamido Ligands , 2011 .

[13]  Z. Hou,et al.  Scandium-Catalyzed Regio- and Stereospecific cis-1,4-Polymerization of 1,3-Cyclohexadiene and Copolymerization with Ethylene , 2010 .

[14]  R. Anwander,et al.  Homoleptic rare-earth metal complexes containing Ln-C σ-bonds. , 2010, Chemical reviews.

[15]  Dongmei Cui,et al.  CCC-Pincer Bis(carbene) Lanthanide Dibromides. Catalysis on Highly cis-1,4-Selective Polymerization of Isoprene and Active Species , 2010 .

[16]  Z. Hou,et al.  Living catalyzed-chain-growth polymerization and block copolymerization of isoprene by rare-earth metal allyl precursors bearing a constrained-geometry-conformation ligand. , 2010, Chemical communications.

[17]  Z. Hou,et al.  Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls. , 2010, Nature chemistry.

[18]  Lihong Hu,et al.  Alternating and random copolymerization of isoprene and ethylene catalyzed by cationic half-sandwich scandium alkyls. , 2009, Journal of the American Chemical Society.

[19]  Z. Hou,et al.  Cationic scandium allyl complexes bearing mono(cyclopentadienyl) ligands: synthesis, novel structural variety, and olefin-polymerization catalysis. , 2008, Chemistry, an Asian journal.

[20]  B. Vuillemin,et al.  Stereocontrolled styrene–isoprene copolymerization and styrene–ethylene–isoprene terpolymerization with a single-component allyl ansa-neodymocene catalyst , 2008 .

[21]  F. Bertini,et al.  Butadiene-isoprene copolymerization with V(acac)3-MAO. Crystalline and amorphoustrans-1,4 copolymers , 2007 .

[22]  Z. Hou,et al.  Cationic scandium aminobenzyl complexes. Synthesis, structure and unprecedented catalysis of copolymerization of 1-hexene and dicyclopentadiene. , 2007, Chemical communications.

[23]  A. Grassi,et al.  Copolymerization of Styrene with Butadiene and Isoprene Catalyzed by the Monocyclopentadienyl Titanium Complex Ti(η5-C5H5)(η2-MBMP)Cl , 2007 .

[24]  M. Tamm,et al.  Efficient Direct Synthesis of Tropidinyl Titanium and Zirconium Complexes by Allylic CH-Activation of 8-Methyl-8-azabicyclo[3.2.1]oct-2-ene (Tropidine) , 2007 .

[25]  T. Schmalz,et al.  Reversible chain transfer between organoyttrium cations and aluminum: synthesis of aluminum-terminated polyethylene with extremely narrow molecular-weight distribution. , 2006, Chemistry.

[26]  H. Braunschweig,et al.  Constrained geometry complexes—Synthesis and applications , 2006 .

[27]  F. Perdih,et al.  Structure−Reactivity Relationships in Rare-Earth Metal Carboxylate-Based Binary Ziegler-Type Catalysts , 2006 .

[28]  U. Thewalt,et al.  Site selective ligand modification and tactic variation in polypropylene chains produced with metallocene catalysts , 2006 .

[29]  N. Coville,et al.  Group 4 metallocene polymerisation catalysts: quantification of ring substituent steric effects , 2006 .

[30]  R. Duchateau,et al.  “Bound but Not Gagged”Immobilizing Single-Site α-Olefin Polymerization Catalysts , 2005 .

[31]  Yi Luo,et al.  Unprecedented isospecific 3,4-polymerization of isoprene by cationic rare earth metal alkyl species resulting from a binuclear precursor. , 2005, Journal of the American Chemical Society.

[32]  Z. Hou,et al.  Scandium-Catalyzed Copolymerization of Ethylene with Dicyclopentadiene and Terpolymerization of Ethylene, Dicyclopentadiene, and Styrene , 2005 .

[33]  A. Cowley,et al.  The first rare earth organometallic complex of 1,4,7-trithiacyclononane: a precursor to unique cationic ethylene and alpha-olefin polymerisation catalysts supported by an all-sulfur donor ligand. , 2005, Chemical communications.

[34]  V. Monteil,et al.  Alternating copolymerization of ethylene and butadiene with a neodymocene catalyst. , 2005, Angewandte Chemie.

[35]  Benjamin D. Ward,et al.  C3 chirality in polymerization catalysis: a highly active dicationic scandium(III) catalyst for the isoselective polymerization of 1-hexene. , 2005, Angewandte Chemie.

[36]  Z. Hou,et al.  Alternating ethylene-norbornene copolymerization catalyzed by cationic half-sandwich scandium complexes. , 2005, Angewandte Chemie.

[37]  H. Yasuda,et al.  Random and block copolymerizations of norbornene with conjugated 1,3-dienes catalyzed by novel Ni compounds involving N- or O-donated ligands , 2004 .

[38]  N. Ueyama,et al.  Stereospecific Polymerizations of Conjugated Dienes by Single Site Iron Complexes Having Chelating N,N,N-Donor Ligands , 2003 .

[39]  R. Fröhlich,et al.  Biometallorganische Koordinationsverbindungen: Synthese und Strukturen von Übergangsmetallkomplexen mit Tropidinyl- und Tropidin-Liganden† , 2003 .

[40]  V. C. Gibson,et al.  Advances in non-metallocene olefin polymerization catalysis. , 2003, Chemical reviews.

[41]  Steven J Brown,et al.  Synthesis and characterization of titanium complexes containing phosphinimido and tropidinyl ligands: Crystal structure of (trop)(t-Bu3PN)TiCl2 , 2002 .

[42]  W. Piers.  Non-cyclopentadienyl ancillaries in organogroup 3 metal chemistry: a fine balance in ligand design , 2002 .

[43]  T. Ikeda,et al.  Copolymerization of 1,3‐butadiene and isoprene with cobalt dichloride/methylaluminoxane in the presence of triphenylphosphine , 2002 .

[44]  S. Arndt,et al.  Mono(cyclopentadienyl) complexes of the rare-earth metals. , 2002, Chemical reviews.

[45]  F. Bonnet,et al.  Copolymerization of Isoprene with Nonconjugated α,ω−Dienes Using a Single Component Samarocene Catalyst , 2002 .

[46]  F. Bonnet,et al.  New viscoelastic materials obtained by insertion of an α-olefin in a trans-polyisoprene chain with a single-component organolanthanide catalyst , 2001 .

[47]  R. Grubbs,et al.  The development of L2X2Ru=CHR olefin metathesis catalysts: an organometallic success story. , 2001, Accounts of chemical research.

[48]  H. Malinakova,et al.  Enantiocontrolled synthesis of spirooxindoles based on the [5 + 2] cycloaddition of a Tp(CO)(2)Mo(pyridinyl) scaffold (Tp = hydridotrispyrazolylborate). , 2000, Organic letters.

[49]  H. Malinakova,et al.  Enantiocontrolled synthesis of highly functionalized tropanes via [5 + 2] cycloaddition to eta(3)-pyridinylmolybdenum pi-complexes. , 2000, Organic letters.

[50]  T. Marks,et al.  Cocatalysts for metal-catalyzed olefin polymerization: activators, activation processes, and structure-activity relationships. , 2000, Chemical reviews.

[51]  M. Brookhart,et al.  Late-metal catalysts for ethylene homo- and copolymerization. , 2000, Chemical reviews.

[52]  G. Coates.  Precise control of polyolefin stereochemistry using single-site metal catalysts. , 2000, Chemical reviews.

[53]  R. Bergman,et al.  Synthesis of Novel Group 4 Complexes Bearing the Tropidinyl Ligand: Investigations of Dynamic Behavior, Reactivity, and Catalytic Olefin Polymerization , 2000 .

[54]  J. Michl,et al.  Over four hundred million characters served: 99 volumes, 2567 articles, 85623 pages, and more than 85 million words. , 2000, Chemical reviews.

[55]  R. Waymouth,et al.  Group 4 ansa-Cyclopentadienyl-Amido Catalysts for Olefin Polymerization. , 1998, Chemical reviews.

[56]  R. Bergman,et al.  Synthesis, Structural Characterization, and Reactivity of Novel Zirconium(IV) Complexes Containing the Tropidinyl Ligand , 1997 .

[57]  M. Marques,et al.  Copolymerization of ethylene and butadiene with a Ziegler catalyst based on MgH2/TiCl4 , 1994 .

[58]  W. Kaminsky,et al.  Elastomers by atactic linkage of α-olefins using soluble Ziegler catalysts , 1986 .