English   español  
Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/93420
logo share SHARE logo core CORE   Add this article to your Mendeley library MendeleyBASE

Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar a otros formatos:

Nickel and Palladium Complexes with New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts

AuthorsOrtiz de la Tabla, Laura; Matas, Inmaculada ; Palma, Pilar ; Álvarez, Eleuterio ; Cámpora, Juan
Issue DateJan-2013
PublisherAmerican Chemical Society
CitationOrganometallics, 31(3): 1006-1016 (2012)
AbstractPhosphinito-imines, a new class of P,N donors, are readily generated by reaction of bulky arylamide anions [R2CONAr]− (R2 = Me or t-Bu; Ar = 2,6-i-Pr2C6H4) with chlorophosphines ClP(R1)2. In solution, free phosphinito-imines exist in equilibrium with the corresponding amidophosphine tautomers, containing a nitrogen-bound P(R1)2 group. However, reacting the tautomer mixtures with metal precursor complexes, such as NiBr2(dme) or PdCl2(cod), selectively affords stable phosphinito-imine complexes MX2(P-N) (M = Ni, Pd) in excellent yields. These complexes are diamagnetic and exhibit square-planar structures in the solid state, but in solution, the Ni derivatives exchange with a small amount of the corresponding high-spin tetrahedral isomers. On treatment with MMAO or DEAC, NiX2(P-N) complexes become active ethylene oligomerization catalysts, affording mainly butenes along with smaller amounts of hexenes and octenes. The activity and the selectivity of these catalysts depend on the structure of the phosphinito-imine ligand and the cocatalyst used. When activated with DEAC, complexes containing the P(i-Pr)2 moiety are extremely active, achieving TOFs over 106 mol C2H4/mol Ni·h and high selectivity for butenes
Publisher version (URL)http://dx.doi.org/10.1021/om201088y
Appears in Collections:(IIQ) Artículos
Files in This Item:
File Description SizeFormat 
Organometalllics.pdf529,24 kBAdobe PDFThumbnail
Show full item record

Related articles:

WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.