A Selective Chromium Catalyst System for the Trimerization of Ethene and Its Coordination Chemistry

In this paper a novel ligand of the type [PNPNH] is presented for the application in a new homogeneous highly selective ethene trimerization system for the formation of 1-hexene, which consists of the chromium source CrCl 3 (thf) 3 , the ligand Ph 2 PN(iPr)P(Ph)N(iPr)H (1), and Et 3 Al as an activator in toluene. The excellent characteristics of this new system, e.g. very high selectivity to C 6 with highest purity of the C 6 fraction (>99 % 1-hexene), activity on a constant level on a long timescale, use of small amounts of Et 3 Al as a cheap activator, and only very low production of PE, make it to a hot candidate for industrial application. Its organometallic background gives an indication of the nature of the active catalyst species.

[1]  S. Gambarotta,et al.  Isolation of a self-activating ethylene trimerization catalyst. , 2009, Angewandte Chemie.

[2]  T. Hor,et al.  Crystallographic Revelation of the Role of AlMe3 (in MAO) in Cr [NNN] Pyrazolyl Catalyzed Ethylene Trimerization , 2009 .

[3]  Stephan Peitz,et al.  Reaction kinetics of the ethene tetramerization catalyst system CrCl3(THF)3, Ph2PN(iPr)PPh2 and MAO: The unexpected and unusual formation of odd-numbered 1-olefins , 2009 .

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

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

[6]  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.

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

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

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

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

[11]  M. Parvez,et al.  Formation of a chiral NPPN ligand via metallation of acyclic NPNCN systems. , 2004, Chemical communications.

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

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

[14]  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.

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

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

[17]  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.

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

[19]  Takashi Monoi,et al.  Silica-supported Cr[N(SiMe3)2]3/isobutylalumoxane catalyst for selective ethylene trimerization , 2002 .

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

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

[22]  W. E. Walker,et al.  A soluble chromium-based catalyst for ethylene trimerization and polymerization , 1977 .