Insights into the spin-forbidden reaction between L2Pd0 and molecular oxygen

被引：89

作者：

Landis, CR ^{[1
]}

Morales, CM ^{[1
]}

Stahl, SS ^{[1
]}

机构：

[1] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 50期

关键词：

D O I：

10.1021/ja044674b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction between dioxygen and palladium(0) is a key step in palladium-catalyzed aerobic oxidation reactions. The spin-forbidden reaction between (en)Pd and O2 has been analyzed by spin-unrestricted density functional methods and shown to proceed by a stepwise process involving (1) formation of a triplet η1-superoxo-PdI adduct, (2) spin-crossover from the triplet to the singlet surface, and (3) collapse of the singlet η1-superoxo-PdI adduct into an η2-peroxo-PdII complex. Delocalization of spin density from triplet O2 onto the palladium center in the first step reduces the exchange interaction between the unpaired spins and facilitates crossover from the triplet to singlet surface. Copyright © 2004 American Chemical Society.

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页码：16302 / 16303

页数：2

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