Allyl Palladium Complexes of Cycloheptatrienyl‐Cyclopentadienyl Phosphane Ligands in Buchwald‐Hartwig Amination Reactions
A series of well‐defined palladium allyl chloride pre‐catalysts was synthesized using previously reported troticenyl phosphane ligands [(η7‐C7H7)Ti(η5‐C5H4PR2)] and [(η7‐C7H6PR2)Ti(η5‐C5H5)] (R = Cy, tBu) as ancillary ligands. The formation of a dimeric µ‐chloro‐, µ‐allyl‐bridged PdI species was obs...
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Veröffentlicht in: | European journal of inorganic chemistry 2019-06, Vol.2019 (21), p.2569-2576 |
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Sprache: | eng |
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Zusammenfassung: | A series of well‐defined palladium allyl chloride pre‐catalysts was synthesized using previously reported troticenyl phosphane ligands [(η7‐C7H7)Ti(η5‐C5H4PR2)] and [(η7‐C7H6PR2)Ti(η5‐C5H5)] (R = Cy, tBu) as ancillary ligands. The formation of a dimeric µ‐chloro‐, µ‐allyl‐bridged PdI species was observed with the ligand [(η7‐C7H7)Ti(η5‐C5H4PtBu2)], whereas L2Pd0 {L = [(η7‐C7H6PtBu2)Ti(η5‐C5H5)]} was formed in presence of KOtPent. In addition, the catalytic activity of the palladium allyl chloride pre‐catalysts was investigated in Buchwald‐Hartwig amination reactions with various aryl halogenides and N‐methylaniline or morpholine. The cyclohexyl derivatives show almost no catalytic activity, whereas for the tert‐butyl derivatives a significant difference could be observed, depending on whether the seven‐membered ring or the five‐membered ring is functionalized.
Palladium allyl chloride complexes containing troticenyl phosphane ligands [(η7‐C7H7)Ti(η5‐C5H4PR2)] and [(η7‐C7H6PR2)Ti(η5‐C5H5)] (R = Cy, tBu) as ancillary ligands were prepared and used as pre‐catalysts for Buchwald‐Hartwig amination reactions. |
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ISSN: | 1434-1948 1099-0682 |
DOI: | 10.1002/ejic.201900225 |