Abstract
AbstractThe tertiary phosphane Ph2P‐pzONa, in which the phosphorus atom is substituted by an electron‐withdrawing pyrazol‐onato unit, reacts with trans‐[NiPhCl(PPh3)2] to afford quan‐titatively trans‐P,P'‐[NiPh(Ph2P‐pzO)(PPh3)] (4), the first Keim‐type catalyst derived from an amide. In the absence of any cocatalyst, complex 4 converts ethylene in high selectivity and activity into α‐olefins. The product distribution is drastically shifted towards lower oligomers when compared to the outcome of the reaction carried out with the conventional SHOP catalyst. Thus, when operating at 1 bar, over 99 wt.‐% of the oligomers formed are C4–C16 oligomers. In ethylene‐free solvents, 4 was shown to slowly undergo reductive elimination to produce the stabilised phosphorus ylide Ph3P‐pzO (5). Both compounds (4 and 5) were characterised by single‐crystal X‐ray diffraction analyses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
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