Synthesis of Novel Dinuclear Complexes by Olefin Metathesis and Their Use in Olefin Polymerization

オレフィン重合反応において複核金属錯体触媒には，単核金属錯体触媒とは異なる特性が期待される．複核金属錯体の重合触媒の例は少ない上，その大部分は同じ金属中心を複数有するものであった．本研究では，オレフィンメタセシスを利用して二つの金属錯体を結合する新しい方法により種々の複核金属錯体を設計し，それを用いたオレフィンの重合について検討を行った．アルケニル基を有するジルコノセンのメタセシスにより，さまざまな長さの架橋鎖を有する複核ジルコノセン錯体を合成した．単核金属錯体に比べて複核金属錯体はより高い活性を示し，さらに架橋鎖がより短い複核金属錯体のほうが活性が高いことが明らかとなった．ジルコノセン錯体と後期遷移金属錯体とのクロスメタセシスにより得られる異種複核金属錯体を用いたエチレンの重合では，用いる金属の種類に応じて異なる分岐構造をもつポリエチレンが得られること，長鎖分岐を有するポリエチレン生成が認められることを見いだした．後期遷移金属上で生成したエチレンオリゴマーが，前期遷移金属上でエチレンとともに共重合することで，そのような分岐ポリエチレンが生成したと考えられる．

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

[2]  Arjan W. Kleij,et al.  Cooperative multimetallic catalysis using metallosalens. , 2010, Chemical communications.

[3]  Daisuke Takeuchi.  Recent progress in olefin polymerization catalyzed by transition metal complexes: new catalysts and new reactions. , 2010, Dalton transactions.

[4]  M. Kanai,et al.  Recent progress in asymmetric bifunctional catalysis using multimetallic systems. , 2009, Accounts of chemical research.

[5]  G. Erker,et al.  Mastering the third dimension of salicylaldimine-type ligand systems: development of a convenient route to bis("ferrocene-saliminato")zirconium chemistry. , 2008, Chemistry.

[6]  S. Matsunaga,et al.  Catalytic asymmetric synthesis of 2,2-disubstituted terminal epoxides via dimethyloxosulfonium methylide addition to ketones. , 2008, Journal of the American Chemical Society.

[7]  Brandon A. Rodriguez,et al.  Neutral bimetallic nickel(II) phenoxyiminato catalysts for highly branched polyethylenes and ethylene-norbornene copolymerizations , 2008 .

[8]  S. Mecking,et al.  Highly Active Binuclear Neutral Nickel(II) Catalysts Affording High Molecular Weight Polyethylene , 2008 .

[9]  T. Marks,et al.  Bimetallic effects in homopolymerization of styrene and copolymerization of ethylene and styrenic comonomers: scope, kinetics, and mechanism. , 2008, Journal of the American Chemical Society.

[10]  D. Matt,et al.  Calix[4]arene-derived nickel diphosphine complexes for LLDPE synthesis via orthogonal tandem and one-pot catalysis , 2007 .

[11]  Qihui Chen,et al.  Arene-Bridged Salicylaldimine-Based Binuclear Neutral Nickel(II) Complexes: Synthesis and Ethylene Polymerization Activities , 2007 .

[12]  R. S. Mauler,et al.  Tandem action of TpmsNiCl and supported Cp2ZrCl2 catalysts for the production of linear low-density polyethylene , 2006 .

[13]  Wei-Hua Wang,et al.  Binuclear neutral nickel complexes bearing bis(bidentate) salicylaldiminato ligands: Synthesis, structure and ethylene polymerization behavior , 2006 .

[14]  David J. Williams,et al.  Ferrocene-Substituted Bis(imino)pyridine Iron and Cobalt Complexes: Toward Redox-Active Catalysts for the Polymerization of Ethylene , 2006 .

[15]  Shiping Zhu,et al.  Long-chain branching and rheological properties of ethylene-1-hexene copolymers synthesized from ethylene stock by concurrent tandem catalysis , 2005 .

[16]  T. Marks,et al.  Significant Proximity and Cocatalyst Effects in Binuclear Catalysis for Olefin Polymerization , 2005 .

[17]  T. Marks,et al.  Coordination copolymerization of severely encumbered isoalkenes with ethylene: enhanced enchainment mediated by binuclear catalysts and cocatalysts. , 2005, Journal of the American Chemical Society.

[18]  Li-Ming Tang,et al.  Synthesis and Ethylene Polymerization Activity of a Novel, Highly Active Single-Component Binuclear Neutral Nickel(II) Catalyst , 2005 .

[19]  K. Osakada,et al.  Zr/Zr and Zr/Fe dinuclear complexes with flexible bridging ligands. preparation by olefin metathesis reaction of the mononuclear precursors and properties as polymerization catalysts , 2005 .

[20]  S. Obrey,et al.  Concurrent tandem catalysis. , 2005, Chemical reviews.

[21]  K. Osakada,et al.  Synthesis and properties of Zr–Co heterodinuclear complexes with a bridging bis(cyclopentadienyl) ligand , 2005 .

[22]  Makoto Watanabe,et al.  Novel Azaferrocenyliminonickel Catalysts for Olefin Polymerization , 2005 .

[23]  T. Marks,et al.  Covalently Linked Heterobimetallic Catalysts for Olefin Polymerization , 2004 .

[24]  T. Marks,et al.  Polynuclear olefin polymerization catalysis: proximity and cocatalyst effects lead to significantly increased polyethylene molecular weight and comonomer enchainment levels. , 2004, Angewandte Chemie.

[25]  K. Hirata,et al.  Olefin Polymerization Catalyzed by Titanium−Tungsten Heterobimetallic Dinitrogen Complexes1 , 2004 .

[26]  T. Marks,et al.  Bimetallic catalysis for styrene homopolymerization and ethylene-styrene copolymerization. Exceptional comonomer selectivity and insertion regiochemistry. , 2004, Journal of the American Chemical Society.

[27]  T. Marks,et al.  Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization. Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts. , 2003, Journal of the American Chemical Society.

[28]  G. Erker,et al.  Formation of dinuclear titanium and zirconium complexes by olefin metathesis--catalytic preparation of organometallic catalyst systems. , 2003, Chemistry.

[29]  K. Osakada,et al.  Reaction of AlMe3 with Heterobimetallic Zr/Rh Complexes Having a C5H4-CMe2-Ind (or C5H4-CMe2-C5H4) Ligand. Formation of Complexes with a Zr−Indenyl (or Zr−Cyclopentadienyl) σ-Bond , 2003 .

[30]  M. Ogasawara,et al.  Synthesis of 1,1‘-Diphospha[4]ferrocenophanes by Molybdenum-Catalyzed Ring-Closing Metathesis , 2003 .

[31]  G. Erker,et al.  Synthesis, Structural and Chemical Characterization of Unsaturated C4‐ and C10‐Bridged Group‐4 ansa‐Metallocenes Obtained Through a Ring‐Closing Olefin Metathesis Reaction , 2002 .

[32]  M. Ogasawara,et al.  Metathesis route to bridged metallocenes. , 2002, Journal of the American Chemical Society.

[33]  C. Richards,et al.  A rapid approach to ferrocenophanes via ring-closing metathesis , 2001 .

[34]  G. Bazan,et al.  Synthesis of Branched Polyethylene by Tandem Catalysis , 2001 .

[35]  Y. Yamaguchi,et al.  Synthesis of ansa-Zirconocene/Rhodium Heterobimetallic Complexes: Enhanced Catalytic Activity in Stereospecific Polymerization of α-Olefins , 1999 .

[36]  Tohru Yamada,et al.  Novel Zirconium-Iron Multinuclear Complex Catalysts for Olefin Polymerizations , 1996 .

[37]  M. Sawamura,et al.  An Enantioselective Two-Component Catalyst System: Rh−Pd-Catalyzed Allylic Alkylation of Activated Nitriles , 1996 .