期刊
ORGANOMETALLICS
卷 28, 期 8, 页码 2372-2384出版社
AMER CHEMICAL SOC
DOI: 10.1021/om801103p
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资金
- National Science Foundation [CHE-0615794]
[(2-R-allyl)M(arene)](+) complexes (M = Pd, Ni; R = H, CH3, CI; arene = mesitylene, hexamethylbenzene) have been synthesized via halide abstraction from the corresponding allyl halide dimers, [(allyl)MX](2), using either AgSbF6 in the case of M = Pd or NaB(Arf)(4) (Ar-f = 3,5-(CF3)(2)C6H3) in the case of M = Ni. The [(allyl)Ni(mesitylene)](+) and [(2-methallyl)Ni(hexamethylbenzene)](+) salts have been characterized by single-crystal X-ray diffraction. The arene ligands in the Pd species are highly labile. The mesitylene ligand in the [(2-R-allyl)Pd(mesitylene)](+) complexes is rapidly displaced at temperatures as low as -120 degrees C by olefins and alkynes (ethylene, tert-butylethylene, cyclopentene, cyclohexene, cyclooctene, 2-butyne) to yield the bis-olefin or bis-alkyne complexes, which have been characterized by NMR spectroscopy. [(allyl)Pd(mesitylene)](+) undergoes rapid degenerate exchange with free mesitylene at low temperatures (Delta G(double dagger) = 1.0.2 kcal/mol). The arene ligand of the Ni complexes is less labile. Displacement of mesitylene from [(allyl)Ni(mesitylene)](+) by excess diethyl ether at 25 degrees C yields [(allyl)Ni(Et2O)(2)](+). Reaction of the [(2-R-allyl)Ni(mesitylene)](+) complexes (R = H, CH3) with alpha-olefins at 25 degrees C yields new allyl complexes plus propene (when R = H) or isobutylene (when R = CH3). A mechanism involving intramolecular hydrogen migration is proposed to account for these transformations.
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