2‐Benzoxazolyl‐6‐[1‐(arylimino)ethyl]pyridyliron(II) Chlorides as Ethylene Oligomerization Catalysts

A series of iron(II) dichloride complexes (Fe 1 –Fe 7 ) ligated by 2-(2-benzoxazolyl)-6-[1-(arylimino)ethyl]pyridines was synthesized and characterized [aryl = 2,6-R12C6H3; R1 = Me ( 1 ), Et ( 2 ), iPr ( 3 ), Cl ( 4 ), Br ( 5 ); 2,6-Me2C6H2-4-R2, R2 = Me ( 6 ), Br ( 7 )]. The molecular structures of Fe 1 , Fe 3 , and Fe 5 were determined by the single-crystal X-ray diffraction. Complexes Fe 1 and Fe 3 both display distorted trigonal-bipyramidal geometries, whereas complex Fe 5 is a distorted square pyramid. Upon activation with modified methylaluminoxane, all iron complexes showed moderate to good activities [up to ca. 106 g(product)?×?(mol Fe)–1 h–1?bar–1] for the oligomerization and polymerization of ethylene, with high selectivity for vinyl-terminated oligomers or polyethylene waxes.

[1]  Wen‐Hua Sun,et al.  2-(1H-2-Benzimidazolyl)-6-(1-(arylimino)ethyl)pyridyl Iron(II) and Cobalt(II) Dichlorides: Syntheses, Characterizations, and Catalytic Behaviors toward Ethylene Reactivity , 2009 .

[2]  Wen‐Hua Sun,et al.  2-Oxazoline/benzoxazole-1,10-phenanthrolinylmetal (iron, cobalt or nickel) dichloride : Synthesis, characterization and their catalytic reactivity for the ethylene oligomerization , 2008 .

[3]  G. Erker,et al.  Bis(iminoethyl)pyridine Systems with a Pendant Alkenyl Group. Part A: Cobalt and Iron Complexes and Their Catalytic Behavior† , 2008 .

[4]  Fosong Wang,et al.  Nickel(II) Complexes Chelated by 2-Arylimino-6-benzoxazolylpyridine: Syntheses, Characterization, and Ethylene Oligomerization , 2008 .

[5]  Wen‐Hua Sun,et al.  2-(1-Isopropyl-2-benzimidazolyl)-6-(1-aryliminoethyl)pyridyl transition metal (Fe, Co, and Ni) dichlorides: Syntheses, characterizations and their catalytic behaviors toward ethylene reactivity , 2008 .

[6]  Wen‐Hua Sun,et al.  Iron(II) and cobalt(II) complexes bearing N-((pyridin-2-yl)methylene)-quinolin-8-amine derivatives: Synthesis and application to ethylene oligomerization , 2008 .

[7]  Wen‐Hua Sun,et al.  Our variations on iron and cobalt catalysts toward ethylene oligomerization and polymerization , 2008 .

[8]  A. Ionkin,et al.  High-Temperature Catalysts for the Production of α-Olefins Based on Iron(II) and Cobalt(II) Tridentate Bis(imino)pyridine Complexes with a Double Pattern of Substitution: o-Methyl plus o-Fluorine in the Same Imino Arm† , 2008 .

[9]  Wen‐Hua Sun,et al.  2-(Benzimidazol-2-yl)-1,10-phenanthrolyl metal (Fe and Co) complexes and their catalytic behaviors toward ethylene oligomerization , 2008 .

[10]  Wen‐Hua Sun,et al.  Unsymmetric bimetal(II) complexes : Synthesis, structures and catalytic behaviors toward ethylene , 2007 .

[11]  Wen‐Hua Sun,et al.  Synthesis and characterization of iron and cobalt dichloride bearing 2-quinoxalinyl-6-iminopyridines and their catalytic behavior toward ethylene reactivity , 2007 .

[12]  G. Giambastiani,et al.  Synthesis of a New Polydentate Ligand Obtained by Coupling 2,6-Bis(imino)pyridine and (Imino)pyridine Moieties and Its Use in Ethylene Oligomerization in Conjunction with Iron(II) and Cobalt(II) Bis-halides , 2007 .

[13]  G. Giambastiani,et al.  Synthesis of New Polydentate Nitrogen Ligands and Their Use in Ethylene Polymerization in Conjunction with Iron(II) and Cobalt(II) Bis-halides and Methylaluminoxane , 2007 .

[14]  Tianfu Liu,et al.  Iron(II) complexes ligated by 2-imino-1,10-phenanthrolines: Preparation and catalytic behavior toward ethylene oligomerization , 2007 .

[15]  G. Solan,et al.  Bis(imino)pyridines: surprisingly reactive ligands and a gateway to new families of catalysts. , 2007, Chemical reviews.

[16]  Wen‐Hua Sun,et al.  Iron(II) and Cobalt(II) 2-(Benzimidazolyl)-6-(1-(arylimino)ethyl)pyridyl Complexes as Catalysts for Ethylene Oligomerization and Polymerization , 2007 .

[17]  Wen‐Hua Sun,et al.  Bimetallic (Iron or Cobalt) Complexes Bearing 2-Methyl-2,4-bis(6-iminopyridin-2-yl)-1H-1,5-benzodiazepines for Ethylene Reactivity , 2007 .

[18]  F. Vizza,et al.  Electronic influence of the thienyl sulfur atom on the oligomerization of ethylene by cobalt(II) 6-(thienyl)-2-(imino)pyridine catalysis , 2007 .

[19]  F. Pelascini,et al.  Modified Pyridine-Bis(imine) Iron and Cobalt Complexes: Synthesis, Structure, and Ethylene Polymerization Study , 2006 .

[20]  G. Mantovani,et al.  Ethylene oligomerization, homopolymerization and copolymerization by iron and cobalt catalysts with 2,6-(bis-organylimino)pyridyl ligands , 2006 .

[21]  Junxian Hou,et al.  Synthesis, Characterization, and Ethylene Oligomerization and Polymerization of [2,6-Bis(2-benzimidazolyl)pyridyl]chromium Chlorides , 2006 .

[22]  R. Fröhlich,et al.  Iron complexes bearing 2-imino-1,10-phenanthrolinyl ligands as highly active catalysts for ethylene oligomerization , 2006 .

[23]  Yi Zheng,et al.  Fe(II) and Co(II) pyridinebisimine complexes bearing different substituents on ortho- and para-position of imines : synthesis, characterization and behavior of ethylene polymerization , 2005 .

[24]  Jean‐Didier Maréchal,et al.  Flexible N,N,N-chelates as supports for iron and cobalt chloride complexes; synthesis, structures, DFT calculations and ethylene oligomerisation studies. , 2004, Dalton transactions.

[25]  Biao Wu,et al.  Synthesis, Characterization, and Ethylene Oligomerization and Polymerization of Ferrous and Cobaltous 2-(Ethylcarboxylato)-6-iminopyridyl Complexes , 2004 .

[26]  Xiaozhen Yang,et al.  Influence of electronic effect on catalytic activity of bis(imino)pyridyl Fe(II) and bis(imino)pyrimidyl Fe(II) complexes , 2004 .

[27]  M. Carney,et al.  New Chromium Complexes for Ethylene Oligomerization: Extended Use of Tridentate Ligands in Metal-Catalyzed Olefin Polymerization , 2004 .

[28]  孙杰,et al.  Halogen-Substituted 2,6-Bis(imino)pyridyl Iron and Cobalt Complexes: Highly Active Catalysts for Polymerization and Oligomerization of Ethylene , 2003 .

[29]  B. Small.  Tridentate Cobalt Catalysts for Linear Dimerization and Isomerization of α-Olefins , 2003 .

[30]  G. Mantovani,et al.  Selective Oligomerization of Ethylene to Linear α-Olefins by Tetrahedral Cobalt(II) Complexes with 6-(Organyl)-2-(imino)pyridyl Ligands: Influence of the Heteroatom in the Organyl Group on the Catalytic Activity , 2003 .

[31]  David J. Williams,et al.  Iron and cobalt ethylene polymerization catalysts: variations on the central donor. , 2003, Inorganic chemistry.

[32]  G. Mantovani,et al.  Oligomerisation of Ethylene to Linear α‐Olefins by new Cs‐ and C1‐Symmetric [2,6‐Bis(imino)pyridyl]iron and ‐cobalt Dichloride Complexes , 2003 .

[33]  David J. Williams,et al.  The role of bulky substituents in the polymerization of ethylene using late transition metal catalysts: a comparative study of nickel and iron catalyst systems , 2003 .

[34]  Jie Sun,et al.  Fluoro-Substituted 2,6-Bis(imino)pyridyl Iron and Cobalt Complexes: High-Activity Ethylene Oligomerization Catalysts , 2003 .

[35]  Xiubing Li,et al.  Ethylene polymerization by iron complexes with symmetrical and unsymmetrical ligands , 2002 .

[36]  You-liang Hu,et al.  Late transition metal complexes bearing 2,9-bis(imino)-1,10-phenanthrolinyl ligands: synthesis, characterization and their ethylene activity , 2002 .

[37]  D. Stephan,et al.  Iron Phosphinimide and Phosphinimine Complexes: Catalyst Precursors for Ethylene Polymerization , 2002 .

[38]  H. Ren,et al.  Ethylene oligomerization by diimine iron(II) complexes/EAO , 2000 .

[39]  Y. Imanishi,et al.  Ethylene Polymerization Catalyzed by Ruthenium and Iron Complexes Containing 2,6-Bis(2-oxazolin-2-yl)pyridine (Pybox) Ligand-Cocatalyst System , 2000 .

[40]  Gregory A. Solan,et al.  IRON AND COBALT ETHYLENE POLYMERIZATION CATALYSTS BEARING 2,6-BIS(IMINO)PYRIDYL LIGANDS : SYNTHESIS, STRUCTURES, AND POLYMERIZATION STUDIES , 1999 .

[41]  Y. Imanishi,et al.  Olefin Polymerization by the (Pybox)RuX2(ethylene)−MAO Catalyst System , 1999 .

[42]  M. Brookhart,et al.  Iron-Based Catalysts with Exceptionally High Activities and Selectivities for Oligomerization of Ethylene to Linear α-Olefins , 1998 .

[43]  Maurice Brookhart,et al.  Highly Active Iron and Cobalt Catalysts for the Polymerization of Ethylene , 1998 .

[44]  Andrew J. P. White,et al.  Novel olefin polymerization catalysts based on iron and cobalt , 1998 .

[45]  A. Aitani,et al.  Ethylene dimerization and oligomerization to butene-1 and linear α-olefins , 1992 .

[46]  G. Henrici-Olivė,et al.  Oligomerization of ethylene with soluble transition-metal catalysts , 1974 .

[47]  P. Flory.  Molecular Size Distribution in Ethylene Oxide Polymers , 1940 .