Lewis acids accelerate reductive elimination of RCN from P2Pd(R)(CN)
Lewis acids accelerate reductive elimination of RCN from P2Pd(R)(CN)
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DOI：
10.1021/om980897x
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发表时间：
1999-02-01
期刊：
影响因子：
2.8
通讯作者：
Moloy, KG
中科院分区：
文献类型：
--
作者：
Huang, JK;Haar, CM;Moloy, KG
配合物dpppPd（CH_2 TMS）（CNER_3）（E = B，Al）的还原消除速率比dpppPd（CH_2 TMS）（CN）快60倍.基于动力学的考虑和CN-和CO的等电子关系，提出了一个迁移型还原消除机制。速率加速与刘易斯酸强度直接相关，后者通过形成反应Pd-CN + ER 3-> Pd-CN-ER 3的刘易斯酸加合物的溶液量热分析测定。
The rate of reductive elimination of the complexes dpppPd(CH2TMS)(CNER3) (E = B, Al) is accelerated up to 60-fold over dpppPd(CH2TMS)(CN). Based on kinetic considerations and the isoelectronic relationship of CN- and CO, a migration-type mechanism for reductive elimination is proposed. The rate acceleration correlates directly with Lewis acid strength, the latter determined by solution calorimetric analyses of the Lewis acid adduct forming reaction Pd-CN + ER3 --> Pd-CN-ER3.