Cp* Chemistry of main-group elements
Cp* Chemistry of main-group elements
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DOI：
10.1039/b001365j
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发表时间：
2000
期刊：
影响因子：
--
通讯作者：
P. Jutzi;Guido Reumann
中科院分区：
文献类型：
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作者：
P. Jutzi;Guido Reumann
在主族元素化学中，五甲基环戊二烯(CP*)是一种非常重要的取代基。由于它的成键方式多种多样，从主要的离子键到主要的共价键，从η5到η2/3到η1，有效地调整各自元素中心的电子状态是可行的。此外，σ或π结合的CP*基团的空间要求能够使其他高活性物种的动力学稳定。共价的Cp*-元素键相对较弱，因此允许快速的S型和触型重排过程。进一步的结果是，Cp*自由基和Cp*−阴离子是潜在的离开基团。这一现象构成了丰富的多面取代和消除化学的基础。作为这一论断的证据，列举了磷、硅和镓化学的几个例子。
In the chemistry of main-group elements the pentamethylcyclopentadienyl (Cp*) group represents a very important substituent. Owing to its quite variable bonding modes, ranging from mainly ionic to mainly covalent and from η5via η2/3 to η1, an effective adjustment to the electronic situation at the respective element centre is feasible. Furthermore, the steric requirements of the σ- or π-bound Cp* group enable the kinetic stabilization of otherwise highly reactive species. Covalent Cp*–element bonds are comparatively weak, consequently allowing fast sigmatropic and haptotropic rearrangement processes. A further consequence is that the Cp* radical as well as the Cp*− anion are potential leaving groups. This phenomenon forms the basis of a rich faceted substitution and elimination chemistry. As proof of this statement, several examples from phosphorus, silicon, and gallium chemistry are presented.