Exceedingly Facile Ph?X Activation (X=Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms
Exceedingly Facile Ph?X Activation (X=Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms
复制标题
用钌 (II) 极其简单地激活 Ph?X（X=Cl、Br、I）：抑制动力学、自催化和机制
DOI：
10.1002/ange.201501996
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发表时间：
2015
影响因子：
--
通讯作者：
Miloserdov F
中科院分区：
文献类型：
--
作者：
Miloserdov F
[(Ph3P)3Ru(L)(H)2] (where L=H2(1) in the presence of styrene, Ph3P (3), and N2(4)) cleave the PhX bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from3and4. The reaction of3with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex2, originating from the initial PhI activation with3, is roughly as reactive toward PhI as3itself; and 2) the PhI bond cleavage with the just‐produced2gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still‐present3to recover2. Both the initial and onward activation reactions involve PPh3dissociation, PhI coordination to Ru through I, rearrangement to a η2‐PhI intermediate, and PhI oxidative addition.
