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首页> 外文期刊>Organometallics >Catalytic hydroalkylation of olefins by stabilized carbon nucleophiles promoted by dicationic platinum(II) and palladium(II) complexes
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Catalytic hydroalkylation of olefins by stabilized carbon nucleophiles promoted by dicationic platinum(II) and palladium(II) complexes

机译：阳离子铂（II）和钯（II）配合物促进的稳定碳亲核试剂对烯烃的催化加氢烷基化

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摘要

The coordinated olefin in dicationic platinum(II) and palladium(II) complexes [M(PNP)(olefin)](SbF_6)_2 (M = Pt, Pd; PNP = 2,6-bis(diphenylphosphinomethyl)pyridine; olefin = ethylene, propylene) reacts with β-dicarbonyl compounds (pentane-2,4-dione and methyl-3-oxobutanoate). If the proton released after the nucleophilic attack is trapped by a base, stable σ-alkyl derivatives [(PNP)M-CH_2-CH(R)CH(Ac)COR′] SbF_6 (R = H, Me; R′ = Me, OMe) are formed; otherwise the M-C σ-bond can be cleaved by the proton, in the rate-determining step of a catalytic cycle that leads to the alkylated dicarbonyl compound. The β-diketone is intrinsically more reactive than the β-ketoester, but in the catalytic reaction of the former an inhibition effect is observed in the case of the platinum catalyst.
机译：常规铂（II）和钯（II）配合物中的配位烯烃[M（PNP）（烯烃）]（SbF_6）_2（M = Pt，Pd; PNP = 2,6-双（二苯基膦基甲基）吡啶;烯烃=乙烯，丙烯）与β-二羰基化合物（戊烷-2,4-二酮和3-氧代丁酸甲酯）反应。如果亲核攻击后释放的质子被碱捕获，则稳定的σ-烷基衍生物[（PNP）M-CH_2-CH（R）CH（Ac）COR'] SbF_6（R = H，Me; R'= Me ，OMe）形成;否则，在导致烷基化二羰基化合物的催化循环的速率确定步骤中，M-Cσ键可被质子裂解。 β-二酮本质上比β-酮酯更具反应性，但在前者的催化反应中，在铂催化剂的情况下观察到抑制作用。

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