An Unusual Example of CH Oxidative Addition following Phosphine Association: Mechanism of Formation and Reactivity of Cp*Ru(.mu.-H)(.mu.-.eta.3,.eta.1-iPrNC(Me)CHHagostic)RuCp*
An Unusual Example of CH Oxidative Addition following Phosphine Association: Mechanism of Formation and Reactivity of Cp*Ru(.mu.-H)(.mu.-.eta.3,.eta.1-iPrNC(Me)CHHagostic)RuCp*
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膦缔合后 CH 氧化加成的不寻常实例：Cp*Ru(μ-H)(μ-eta.3,eta.1-iPrNC(Me)CHHagostic)RuCp* 的形成机制和反应性
DOI：
10.1021/om00007a020
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发表时间：
1995
期刊：
影响因子：
2.8
通讯作者：
K. G. Caulton
中科院分区：
文献类型：
--
作者：
R. Kuhlman;K. Folting;K. G. Caulton
0.0408）。LDA在次甲基位置氘代的机理研究表明，该反应的机理是（1）N ′ Pr 2对Cl的复分解，（2）β-CH活化，（3）γ-CH活化，和（4）通过第二当量的LDA脱卤化氢。桥氢化物被发现与两个乙烯基氢交换缓慢。CO取代了1中的agostic相互作用，形成了一个氮杂烯丙基的CO加合物。然而，1与小膦的产物是亚甲基桥连的二聚体，即，在含膦的产物中，agostic相互作用的CH键断裂。
0.0408). Mechanistic studies with LDA deuterated at the methine positions suggest that the mechanism of this reaction is (1) metathesis of N ‘Pr2 for Cl,(2)/3-CH activation,(3) y-CH activation, and (4) dehydrohalogenation by a second equivalent of LDA. The bridging hydride was found to exchange slowly with the two vinyl hydrogens. CO replaces the agostic interaction in 1 to form a CO adduct of a bimetallic azaallyl. However, the products of 1 with smallphosphines are methylidene-bridged dihydrides; ie, the CH bond of the agostic interaction is brokenin the phosphine-containing products.