Ethylene oligomerization using iron complexes: beyond the discovery of bis(imino)pyridine ligands.

Since the discovery that bis(imino)pyridine ligands are able to confer high activities in ethylene oligomerization and polymerization to their iron complexes, considerable attention has been focused on catalyst design for these reactions and this research constitutes an ever-growing area in molecular catalysis. The tuning of the ligand structures and properties, and thus of catalysts, generally represents the basis for subsequent work contributing to process development and industrialization. Significant effort is therefore devoted to generate structural diversity in order to access the required catalyst stability and selectivity. This feature article outlines nitrogen-containing ligands that have been developed for the iron-catalyzed oligomerization of ethylene since the seminal discovery of the properties of bis(imino)pyridine ligands.

[1]  M. W. Bouwkamp,et al.  Electron-deficient iron alkyl complexes supported by diimine ligand (Ph2CN)2C2H4: Evidence for reversible ethylene binding , 2009 .

[2]  R. Kempe,et al.  Sterically Demanding Iminopyridine Ligands , 2007 .

[3]  Wen‐Hua Sun,et al.  Synthesis, characterization and catalytic behavior toward ethylene of 2-[1-(4,6-dimethyl-2-benzhydrylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridylmetal (iron or cobalt) chlorides. , 2013, Dalton transactions.

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

[5]  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 .

[6]  Y. Chauvin,et al.  Influence of intramolecular N-H...O-Ni hydrogen bonding in nickel(II) diphenylphosphinoenolate phenyl complexes on the catalytic oligomerization of ethylene , 2005 .

[7]  W. Keim Nickel: An Element with Wide Application in Industrial Homogeneous Catalysis , 1990 .

[8]  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 .

[9]  Paige Morse,et al.  TAKING A MEASURE OF SUSTAINABILITY , 1999 .

[10]  J. Steed,et al.  Bis(carbene)pyridine Complexes of the Early to Middle Transition Metals: Survey of Ethylene Oligomerization and Polymerization Capability , 2004 .

[11]  Wen‐Hua Sun,et al.  Tailoring iron complexes for ethylene oligomerization and/or polymerization. , 2013, Dalton transactions.

[12]  Fosong Wang,et al.  Synthesis, characterization and catalytic behavior toward ethylene of cobalt(II) and iron(II) complexes bearing 2-(1-aryliminoethylidene)quinolines , 2011 .

[13]  M. Carney,et al.  Alternatives to pyridinediimine ligands: syntheses and structures of metal complexes supported by donor-modified alpha-diimine ligands. , 2007, Dalton transactions.

[14]  H. Olivier-Bourbigou,et al.  Direct synthesis of a new class of N,N,N ligands based on 1,2-dihydro-1,10-phenanthroline backbone and their coordination to Pd complexes. , 2009, Dalton transactions.

[15]  J. Skupińska Oligomerization of .alpha.-olefins to higher oligomers , 1991 .

[16]  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 .

[17]  J. Fischer,et al.  Intramolecular O–H ⋯ O–Ni and N–H ⋯ O–Ni hydrogen bonding in nickel diphenylphosphinoenolate phenyl complexes: role in catalytic ethene oligomerisation; crystal structure of [NiPH{Ph2PCHC(O)(o-C6H4NHPh)}(PPh3)] , 1994 .

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

[19]  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 .

[20]  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 .

[21]  M. Carney,et al.  Oligomerization of Ethylene Using New Tridentate Iron Catalysts Bearing α-Diimine Ligands with Pendant S and P Donors , 2010 .

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

[23]  Cheng Zhang,et al.  Synthesis and Characterization of Iron, Cobalt, and Nickel Complexes Bearing Novel N,N‐Chelate Ligands and Their Catalytic Properties in Ethylene Oligomerization , 2007 .

[24]  Wen‐Hua Sun,et al.  Iron(III) complexes bearing 2-(benzimidazole)-6-(1-aryliminoethyl)pyridines: Synthesis, characterization and their catalytic behaviors towards ethylene oligomerization and polymerization , 2010 .

[25]  Andrew L. Johnson,et al.  Preparation of Linear α-Olefins Using Cationic Nickel(II) α-Diimine Catalysts , 1997 .

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

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

[28]  H. Olivier-Bourbigou,et al.  Novel Catalytic System for Ethylene Oligomerization: An Iron(III) Complex with an Anionic N,N,N Ligand , 2011 .

[29]  Wen‐Hua Sun,et al.  Ferrous and Cobaltous Chlorides Bearing 2,8-Bis(imino)quinolines: Highly Active Catalysts for Ethylene Polymerization at High Temperature , 2010 .

[30]  Wen‐Hua Sun,et al.  Controlling the ethylene polymerization parameters in iron pre-catalysts of the type 2-(1-(2,4-dibenzhydryl-6-methylphenylimino)ethyl)-6-(1-(arylimino)ethyl) pyridyliron dichloride , 2012 .

[31]  D. Stephan,et al.  Pyridine− and Imidazole−Phosphinimine Bidentate Ligand Complexes: Considerations for Ethylene Oligomerization Catalysts , 2003 .

[32]  P. Chirik,et al.  Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes , 2004 .

[33]  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 .

[34]  H. Olivier-Bourbigou,et al.  Oligomerization of Monoolefins by Homogeneous Catalysts , 2009 .

[35]  K. Rypdal,et al.  Synthesis of bis[bis(trimethylsilyl)amido]iron(II). Structure and bonding in M[N(SiMe3)2]2 (M = manganese, iron, cobalt): two-coordinate transition-metal amides , 1988 .

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

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

[38]  Maurice Brookhart,et al.  New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and .alpha.-Olefins , 1995 .

[39]  F. Dahan,et al.  Synthesis of cationic and neutral methallyl nickel complexes and applications in ethene oligomerisation , 1994 .

[40]  Fosong Wang,et al.  2-β-Benzothiazolyl-6-iminopyridylmetal dichlorides and the catalytic behavior towards ethylene oligomerization and polymerization , 2011 .

[41]  G. Erker,et al.  Bidentate Iron(II) Dichloride Complexes Bearing Substituted 8-(Benzimidazol-2-yl)quinolines: Synthesis, Characterization, and Ethylene Polymerization Behavior , 2011 .

[42]  David J. Williams,et al.  Imine Versus Amine Donors in Iron‐Based Ethylene Polymerisation Catalysts , 2001 .

[43]  A. Noels,et al.  Iron(II)–ethylene polymerization catalysts bearing 2,6-bis(imino)pyrazine ligands: Part I. Synthesis and characterization , 2006 .

[44]  Wen‐Hua Sun,et al.  2-Ethyl-ketimino-1,10-phenanthroline iron(II) complexes as highly active catalysts for ethylene oligomerization , 2010 .

[45]  M. Hursthouse,et al.  Chelating and 'pincer' dicarbene complexes of palladium; synthesis and structural studies , 2003 .

[46]  M. Thornton-Pett,et al.  Synthesis and reactivity of sterically hindered iminopyrrolato complexes of zirconium, iron, cobalt and nickel , 2000 .

[47]  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.

[48]  David J. Williams,et al.  Aluminum alkyl-mediated route to novel N,N,O-chelates for five-coordinate Iron(II) chloride complexes: Synthesis, structures, and ethylene polymerization studies , 2007 .

[49]  Joseph A. Wright,et al.  N-Heterocyclic Pincer Dicarbene Complexes of Iron(II): C-2 and C-5 Metalated Carbenes on the Same Metal Center , 2004 .

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

[51]  G. Giambastiani,et al.  Olefin oligomerization, homopolymerization and copolymerization by late transition metals supported by (imino)pyridine ligands , 2010 .

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

[53]  M. Brookhart,et al.  Ethylene Oligomerization and Propylene Dimerization Using Cationic (α-Diimine)nickel(II) Catalysts , 1999 .

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

[55]  M. Carney,et al.  Oligomerization of Ethylene Using New Iron Catalysts Bearing Pendant Donor Modified α-Diimine Ligands , 2007 .

[56]  J. Fawcett,et al.  Substituted N-picolylethylenediamines of the type (ArNHCH2CH2){(2-C5H4N)CH2}NR [R = Me, 4-CH2=CH(C6H4)CH2, (2-C5H4N)CH2] and their transition metal(II) halide complexes. , 2005, Dalton transactions.

[57]  Wen‐Hua Sun,et al.  2‐Arylimino‐9‐phenyl‐1,10‐phenanthrolinyl‐iron, ‐cobalt and ‐nickel Complexes: Synthesis, Characterization and Ethylene Oligomerization Behavior , 2007 .

[58]  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 .

[59]  Fosong Wang,et al.  2‐Benzoxazolyl‐6‐[1‐(arylimino)ethyl]pyridyliron(II) Chlorides as Ethylene Oligomerization Catalysts , 2009 .

[60]  Fosong Wang,et al.  Iron (II) and cobalt(II) complexes bearing 8-(1-aryliminoethylidene) quinaldines: Synthesis, characterization and ethylene dimerization behavior , 2011 .

[61]  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 .

[62]  G. Britovsek,et al.  Thio-Pybox and Thio-Phebox complexes of chromium, iron, cobalt and nickel and their application in ethylene and butadiene polymerisation catalysis. , 2012, Dalton transactions.

[63]  C. Ha,et al.  Iron and Cobalt Complexes of 2,3,7,8-Tetrahydroacridine-4,5(1H,6H)-diimine Sterically Modulated by Substituted Aryl Rings for the Selective Oligomerization to Polymerization of Ethylene , 2011 .

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

[65]  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 .

[66]  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 .

[67]  Wen‐Hua Sun,et al.  Iron-oriented ethylene oligomerization and polymerization: The Iron Age or a flash in the pan , 2011 .

[68]  R. Mulhaupt,et al.  Ethylene homopolymerization with P, O‐chelated nickel catalysts , 1987 .

[69]  D. Matt,et al.  Structure-reactivity relationships in SHOP-type complexes: tunable catalysts for the oligomerisation and polymerisation of ethylene. , 2007, Dalton transactions.

[70]  A. Noels,et al.  Iron(II)–ethylene polymerization catalysts bearing 2,6-bis(imino)pyrazine ligands: Part II. Catalytic behaviour, homogeneous and heterogeneous insights , 2006 .

[71]  M. Leskelä,et al.  Bis(imino)cyclodiphosph(V)azane complexes of late transition metals: Efficient catalyst precursors for ethene and propene oligomerization and dimerization , 2006 .

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

[73]  Andrew J. P. White,et al.  Synthesis and reactivity of 1,8-bis(imino)carbazolide complexes of iron, cobalt and manganese , 2003 .

[74]  K. Ziegler,et al.  XVIII. Addition von Lithium‐alkylen an Äthylen , 1950 .

[75]  You-liang Hu,et al.  Ethylene oligomerization promoted by group 8 metal complexes containing 2-(2-pyridyl)quinoxaline ligands , 2002 .

[76]  P. Braunstein,et al.  Nickel and iron complexes with N,P,N-type ligands: synthesis, structure and catalytic oligomerization of ethylene. , 2008, Dalton transactions.

[77]  Hans-Dieter Martin,et al.  Das Mülheimer Normaldruck‐Polyäthylen‐Verfahren , 1955 .

[78]  Martin J. Hanton,et al.  Ethylene Oligomerization Using First-Row Transition Metal Complexes Featuring Heterocyclic Variants of Bis(imino)pyridine Ligands , 2009 .

[79]  W. Keim,et al.  2-phosphanylphenolate nickel catalysts for the polymerization of ethylene. , 2003, Chemistry.

[80]  K. Ziegler Aluminium‐organische Synthese im Bereich olefinischer Kohlenwasserstoffe , 1952 .