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Ethylene trimerization with mixed-donor ligand (N,P,S) chromium complexes: Effect of ligand structure on activity and selectivity

Citation

McGuinness, DS and Wasserscheid, P and Morgan, DH and Dixon, JT, Ethylene trimerization with mixed-donor ligand (N,P,S) chromium complexes: Effect of ligand structure on activity and selectivity, Organometallics, 24, (4) pp. 552-556. ISSN 0276-7333 (2005) [Refereed Article]

DOI: doi:10.1021/om049168+

Abstract

Methylaluminoxane (MAO)-activated chromium(III) complexes of tridentate PNP and SNS ligands of the form (R2PCH2CH2) 2NR′ (R = alkyl, aryl; R′ = H, Me, benzyl) and (RSCH 2-CH2)2NH (R = alkyl) have been prepared and tested for the trimerization of ethylene to 1-hexene. The effect of P or S donor substitution, nitrogen substitution, and chelate ring size has been examined. Sterically compact and basic P or S groups lead to the highest activities and selectivities, while a secondary amine central donor is crucial for high activity, raising the possibility that deprotonation of this group occurs during catalyst formation. Expanding the chelate ring size by introduction of a propyl spacer on one side of the SNS ligand gives EtSC3H 6N(H)C2H4SEt, which leads to a trimerization catalyst with lower activity. The scope of S-donor-based ligands for ethylene trimerization was further studied by preparing and testing PSP and SPS tridentates of CrIII. These complexes give rise to active oligomerization systems that give product distributions characteristic of both linear chain growth and selective trimerization.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Industrial Chemistry
Objective Division:Manufacturing
Objective Group:Industrial Chemicals and Related Products
Objective Field:Organic Industrial Chemicals (excl. Resins, Rubber and Plastics)
Author:McGuinness, DS (Dr David McGuinness)
ID Code:46827
Year Published:2005
Web of Science® Times Cited:138
Deposited By:Chemistry
Deposited On:2007-09-04
Last Modified:2012-04-20
Downloads:0

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