Polymer-Free Ethylene Oligomerization Using a Pyridine-Based Pincer PNP-Type of Ligand

Di- and trivalent chromium complexes of the pyridine-based ligand [2,6-(Ph2PCH2)2 C5H3N]CrCl3 (1) and {[2,6-(Ph2CH2)2C5H3N]CrCl2}.(THF) (2) and their aluminate aggregates [2,6-(Ph2CH2)2C5H3NCrCl(μ-Cl)AlClMe2] (3), {[(2,6-(Ph2CH2)2C5H3NCrCl(μ-Cl)AlClEt2]}. (toluene)0.5 (4), {2,6-(Ph2CH2)2C5H3NCrEt(μ-Cl)2AlEt2}{AlCl3Et} (5), {2,6-(PPh2CH2) C5H3N (PPh2CH)Al(i-Bu)2(μ-Cl)Cr(μ-Cl)2Al(i-Bu)2}.(toluene)1.5 (6), and {[2,6-(PPh2CH2)2C5H3 N]2Cr} {(μ-Cl)[Al(i-Bu)3]2} (7) were prepared, isolated, and their activities toward ethylene oligomerization tested. While complexes 3, 5, and 6 were directly accessible by reacting catalyst precursor 1 with Me3Al, DEAC, and TIBA, respectively, complexes 4 and 7 were prepared using catalyst precursor 2 with DEAC and TIBA, respectively. All these complexes, with the exception of 7, showed good activities for a polymer-free ethylene oligomerization. Complex 7 contains cationic chromium in its monovalent state and its encapsulation in an octahedral ligand field as defined by two liga...

[1]  Y. Diskin‐Posner,et al.  Anionic nickel(II) complexes with doubly deprotonated PNP pincer-type ligands and their reactivity toward CO2 , 2013 .

[2]  S. Gambarotta,et al.  Aminophosphine-Based Chromium Catalysts for Selective Ethylene Tetramerization , 2012 .

[3]  L. Chen,et al.  Stereospecific polymerization of 1,3-butadiene catalyzed by cobalt complexes bearing N-containing diphosphine PNP ligands , 2012 .

[4]  H. Nakanishi,et al.  Synthesis and Protonation of Molybdenum– and Tungsten–Dinitrogen Complexes Bearing PNP-Type Pincer Ligands , 2012 .

[5]  K. Albahily,et al.  A highly selective ethylene tetramerization catalyst. , 2012, Angewandte Chemie.

[6]  Mathieu J-L Tschan,et al.  New processes for the selective production of 1-octene , 2011 .

[7]  T. Agapie.  Selective ethylene oligomerization: Recent advances in chromium catalysis and mechanistic investigations , 2011 .

[8]  Mohammed H. Al-Hazmi,et al.  Heterobimetallic Al−Cl−Cr Intermediates with Relevance to the Selective Catalytic Ethene Trimerization Systems Consisting of CrCl3(THF)3, the Aminophosphorus Ligands Ph2PN(R)P(Ph)N(R)H, and Triethylaluminum , 2011 .

[9]  D. McGuinness.  Olefin oligomerization via metallacycles: dimerization, trimerization, tetramerization, and beyond. , 2011, Chemical reviews.

[10]  K. Albahily,et al.  A chromium ethylidene complex as a potent catalyst for selective ethylene trimerization. , 2011, Angewandte Chemie.

[11]  D. Wass,et al.  N,N′-Bis(diphenylphosphino)diaminophenylphosphine Ligands for Chromium-Catalyzed Selective Ethylene Oligomerization Reactions , 2011 .

[12]  K. Albahily,et al.  Towards selective ethylene tetramerization. , 2010, Angewandte Chemie.

[13]  Mohammed H. Al-Hazmi,et al.  Activation and deactivation by temperature: behavior of Ph2PN(iPr)P(Ph)N(iPr)H in the presence of alkylaluminum compounds relevant to catalytic selective ethene trimerization. , 2010, Chemistry.

[14]  Minserk Cheong,et al.  Bimetallic Ethylene Tetramerization Catalysts Derived from Chiral DPPDME Ligands: Syntheses, Structural Characterizations, and Catalytic Performance of [(DPPDME)CrCl3]2 (DPPDME = S,S- and R,R-chiraphos and meso-achiraphos) , 2010 .

[15]  S. Gambarotta,et al.  Switchable chromium(II) complexes of a chelating amidophosphine (N-P) for selective and nonselective ethylene oligomerization , 2010 .

[16]  Mohammed H. Al-Hazmi,et al.  Coordination chemistry of new selective ethylene trimerisation ligand Ph2PN(iPr)P(Ph)NH(R) (R = iPr, Et) and tests in catalysis. , 2010, Dalton transactions.

[17]  Mohammed H. Al-Hazmi,et al.  An alternative mechanistic concept for homogeneous selective ethylene oligomerization of chromium-based catalysts: binuclear metallacycles as a reason for 1-octene selectivity? , 2010, Chemistry.

[18]  Mohammed H. Al-Hazmi,et al.  Metalation and Transmetalation Studies on Ph2PN(iPr)P(Ph)N(iPr)H for Selective Ethene Trimerization to 1-Hexene⊥ , 2010 .

[19]  Bernd H. Müller,et al.  A Selective Chromium Catalyst System for the Trimerization of Ethene and Its Coordination Chemistry , 2010 .

[20]  L. Magna,et al.  PCNCP ligands in the chromium-catalyzed oligomerization of ethylene: tri- versus tetramerization. , 2009, Chemistry.

[21]  Sudhir A. Kulkarni,et al.  Density functional studies on chromium catalyzed ethylene trimerization , 2009 .

[22]  P. Budzelaar.  Ethene trimerization at CrI/CrIII — A density functional theory (DFT) study , 2009 .

[23]  C. Mason,et al.  Isolation of single-component trimerization and polymerization chromium catalysts: the role of the metal oxidation state. , 2008, Angewandte Chemie.

[24]  S. Gambarotta,et al.  Preparation and Characterization of a Switchable Single-Component Chromium Trimerization Catalyst , 2008 .

[25]  P. Braunstein,et al.  Highly Selective Chromium(III) Ethylene Trimerization Catalysts with [NON] and [NSN] Heteroscorpionate Ligands , 2008 .

[26]  K. Albahily,et al.  Chromium catalysts supported by a nonspectator NPN ligand: isolation of single-component chromium polymerization catalysts. , 2008, Angewandte Chemie.

[27]  A. Spek,et al.  T-shaped cationic CuI complexes with hemilabile PNP-type ligands. , 2008, Inorganic chemistry.

[28]  A. Slawin,et al.  Carbon-bridged diphosphine ligands for chromium-catalysed ethylene tetramerisation and trimerisation reactions , 2008 .

[29]  Sai Zhang,et al.  The effect of N-aryl bisphosphineamine ligands on the selective ethylene tetramerization , 2008 .

[30]  G. Sheldrick.  A short history of SHELX. , 2008, Acta crystallographica. Section A, Foundations of crystallography.

[31]  T. Agapie,et al.  Mechanistic studies of olefin and alkyne trimerization with chromium catalysts: deuterium labeling and studies of regiochemistry using a model chromacyclopentane complex. , 2007, Journal of the American Chemical Society.

[32]  P. Wasserscheid,et al.  Ethylene tetramerisation: Subtle effects exhibited by N-substituted diphosphinoamine ligands , 2007 .

[33]  P. Wasserscheid,et al.  The use of bis(diphenylphosphino)amines with N-aryl functionalities in selective ethylene tri-and tetramerisation , 2007 .

[34]  A. Orpen,et al.  One electron oxidation of chromium N,N-bis(diarylphosphino)amine and bis(diarylphosphino)methane complexes relevant to ethene trimerisation and tetramerisation. , 2007, Dalton transactions.

[35]  Duncan F Wass,et al.  Chromium-catalysed ethene trimerisation and tetramerisation--breaking the rules in olefin oligomerisation. , 2007, Dalton transactions.

[36]  P. Wasserscheid,et al.  N-substituted diphosphinoamines: Toward rational ligand design for the efficient tetramerization of ethylene , 2007 .

[37]  A. Slawin,et al.  Ethylene Tri- and Tetramerization with Borate Cocatalysts: Effects on Activity, Selectivity, and Catalyst Degradation Pathways , 2007 .

[38]  J. Berg,et al.  Role of MAO in Chromium-Catalyzed Ethylene Tri- and Tetramerization: A DFT Study , 2007 .

[39]  S. Gambarotta,et al.  The question of the Cr oxidation state in the {Cr(SNS)} catalyst for selective ethylene trimerization: an unanticipated re-oxidation pathway. , 2006, Angewandte Chemie.

[40]  J. Bercaw,et al.  Nitrogen-Linked Diphosphine Ligands with Ethers Attached to Nitrogen for Chromium-Catalyzed Ethylene Tri- and Tetramerizations , 2006 .

[41]  S. Gambarotta,et al.  Role of the metal oxidation state in the SNS-Cr catalyst for ethylene trimerization: isolation of di- and trivalent cationic intermediates. , 2006, Journal of the American Chemical Society.

[42]  J. Bercaw,et al.  Ethylene Trimerization Catalysts Based on Chromium Complexes with a Nitrogen-Bridged Diphosphine Ligand Having ortho-Methoxyaryl or ortho-Thiomethoxy Substituents: Well-Defined Catalyst Precursors and Investigations of the Mechanism , 2006 .

[43]  T. Agapie,et al.  A Chromium-Diphosphine System for Catalytic Ethylene Trimerization: Synthetic and Structural Studies of Chromium Complexes with a Nitrogen-Bridged Diphosphine Ligand with ortho-Methoxyaryl Substituents , 2006 .

[44]  S. Gambarotta,et al.  Isolation of a Cationic Chromium(II) Species in a Catalytic System for Ethylene Tri- and Tetramerization , 2006 .

[45]  S. Gambarotta,et al.  Switchable Chromium(II) Ethylene Oligomerization/Polymerization Catalyst , 2005 .

[46]  Kevin Blann,et al.  Mechanistic investigations of the ethylene tetramerisation reaction. , 2005, Journal of the American Chemical Society.

[47]  M. Döring,et al.  Chromium imine and amine complexes as homogeneous catalysts for the trimerisation and polymerisation of ethylene , 2005 .

[48]  A. Bollmann,et al.  Highly selective chromium-based ethylene trimerisation catalysts with bulky diphosphinoamine ligands. , 2005, Chemical communications.

[49]  P. Wasserscheid,et al.  Ethylene Trimerization with Mixed-Donor Ligand (N,P,S) Chromium Complexes: Effect of Ligand Structure on Activity and Selectivity , 2005 .

[50]  D. H. Morgan,et al.  Advances in selective ethylene trimerisation – a critical overview , 2004 .

[51]  A. Slawin,et al.  Ethylene tetramerization: a new route to produce 1-octene in exceptionally high selectivities. , 2004, Journal of the American Chemical Society.

[52]  K. Stark,et al.  A DFT study toward the mechanism of chromium-catalyzed ethylene trimerization , 2004 .

[53]  T. Agapie,et al.  Mechanistic studies of the ethylene trimerization reaction with chromium-diphosphine catalysts: experimental evidence for a mechanism involving metallacyclic intermediates. , 2004, Journal of the American Chemical Society.

[54]  V. Gokul,et al.  Ethylene trimerisation catalyst based on substituted cyclopentadienes , 2003 .

[55]  S. Schwikkard,et al.  The Effect of Aromatic Ethers on the Trimerisation of Ethylene using a Chromium Catalyst and Aryloxy Ligands , 2003 .

[56]  P. Wasserscheid,et al.  First Cr(III)-SNS complexes and their use as highly efficient catalysts for the trimerization of ethylene to 1-hexene. , 2003, Journal of the American Chemical Society.

[57]  C. Hu,et al.  Novel Cr-PNP complexes as catalysts for the trimerisation of ethylene. , 2003, Chemical communications.

[58]  M. Leskelä,et al.  Iron and Cobalt Complexes of a Series of Tridentate P, N, P Ligands — Synthesis, Characterization, and Application in Ethene Polymerization Reactions , 2002 .

[59]  D. Wass,et al.  High activity ethylene trimerisation catalysts based on diphosphine ligands. , 2002, Chemical Communications.

[60]  P. Wasserscheid,et al.  Selective Trimerization of α-Olefins with Triazacyclohexane Complexes of Chromium as Catalysts. , 2000, Angewandte Chemie.

[61]  D. Lilge,et al.  Triazacyclohexane complexes of chromium as highly active homogeneous model systems for the Phillips catalyst , 2000 .

[62]  R. Blessing,et al.  An empirical correction for absorption anisotropy. , 1995, Acta crystallographica. Section A, Foundations of crystallography.

[63]  J. R. Briggs.  The selective trimerization of ethylene to hex-1-ene , 1989 .