Silylenes: A Unified Picture of Their Stability, Acid-Base and Spin Properties, Nucleophilicity, and Electrophilicity via Computational and Conceptual Density Functional Theory
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- 作者：Julianna Olá ; h ; Tamá ; s Veszpré ; mi ; Frank De Proft ; Paul Geerlings
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：October 25, 2007
- 年：2007
- 卷：111
- 期：42
- 页码：10815 - 10823
- 全文大小：146K
- 年卷期：v.111,no.42(October 25, 2007)
- ISSN：1520-5215
文摘
Conceptual DFT gives sharp definitions for many long-known, but rather vaguely defined chemical concepts.In this study DFT-based reactivity indices are applied to silylenes in order to elucidate the relationshipsamong their properties: stability, acid-base, and spin properties, nucleophilicity and electrophilicity. On thebasis of a detailed, comparative analysis of previously published data, it is shown that the properties of simplesilylenes can be tuned by varying one single factor, the -electron donating ability of the substituents of thesilicon atom leading to well-characterized and systematic changes in the stability/reactivity pattern of themolecule. In order to test the model a series of new compounds are studied: including CH3SiR (where R =CH3, NH2, OH and SH), Si(Si(CH3)3)2, Si(CF3)2 and benzo-, pyrido-, pyridazo-, and pyrimido-anellated-1,3,22-diazasiloles.