Palladium carbene complexes for selective alkene di- and oligomerization

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Title: Palladium carbene complexes for selective alkene di- and oligomerization
Authors: Khlebnikov, Vsevolod
Meduri, Angelo
Müller-Bunz, Helge
Montini, Tiziano
Fornasiero, Paolo
Zangrando, Ennio
Milani, Barbara
Albrecht, Martin
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Date: 13-Jan-2012
Abstract: A series of palladium complexes were synthesized that comprise three sterically different C,N-bidentate coordinating NHC-pyridine ligands (NHC = N-heterocyclic carbene). In one set, the pyridine and the carbene are linked by a flexible CH2 group (a), in the other two sets, the two ligand units are directly linked and feature a shielding mesityl substituent on the carbene and either an unsubstituted pyridine (b) or a xylyl-substituted pyridine unit (c). Investigation of the reactivity of cationic complexes [Pd(C^N)Me(NCMe)]+, 6, analogues to Brookhart’s α-diimine system, towards alkenes showed a strong correlation between the catalytic activity and selectivity and the ligand setting. While 6a was inactive in ethylene conversion, 6b afforded low-molecular weight olefins (oligomerization), and 6c produced exclusively butene (dimerization). With styrene as substrate, exclusive dimerization occurred with all three complexes. Steric and electronic factors were identified that govern the disparate activity and selectivity, and that allow for efficient tailoring of the catalytic performance.
Funding Details: Other funder
Type of material: Journal Article
Publisher: ACS
Journal: Organometallics
Volume: 31
Issue: 3
Start page: 976
End page: 986
Copyright (published version): 2012 American Chemical Society
Keywords: PalladiumN-heterocyclic carbeneEthyleneDimerizationPolymerizationSteric shielding
Subject LCSH: Palladium
Carbenes (Methylene compounds)
DOI: 10.1021/om201027y
Language: en
Status of Item: Peer reviewed
Appears in Collections:Chemistry Research Collection

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