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Carbon monoxide poisoning as a probe for the active site(s) of a nickel-based olefin oligomerization catalyst

✍ Scribed by Linda M Clutterbuck; Leslie D Field; Geoffrey B Humphries; Anthony F Masters; Mark A Williams

Publisher: John Wiley and Sons
Year: 1990
Tongue: English
Weight: 530 KB
Volume: 4
Category: Article
ISSN: 0268-2605
DOI: 10.1002/aoc.590040512

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✦ Synopsis

The interaction of the olefin oligomerization catalyst system derived from [Ni(sacsac)(PBu,)CI] (sacsac = pentane-2,4-dithionate = dithioacetylacetonate) with carbon monoxide (CO) has been examined by a combination of ,'P NMR and FTIR spectroscopy. The catalyst is rapidly and completely inhibited by CO; however, removal of the CO restores catalytic activity. A CO-adduct of the active catalyst has a characteristic CO stretching frequency of 2042cm-', and S3'P 9.9ppm. Carbon monoxide does not react with [Ni(sacsac)(PBu,)CI], but [Ni(sacsac)(PBu,(CI] reacts with any of Et,AICI, BuLi, Li[Et,BH] or K[s-Bu),BH] under an atmosphere of carbon monoxide in the presence or absence of olefin to produce [Ni(PBu,)(CO),], which has been identified by FTIR and NMR. [Ni(sacsac)(PBu,)Cl] reacts completely with BuLi or K[(s-Bu),BH] to form catalytically inactive species which yield active catalysts on addition of Et2AICI.

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