Pyramidanes: The Covalent Form of the Ionic Compounds
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- 作者：Vladimir Ya. Lee ; Olga A. Gapurenko ; Yuki Ito ; Takahiko Meguro ; Haruka Sugasawa ; Akira Sekiguchi ; Ruslan M. Minyaev ; Vladimir I. Minkin ; Rolfe H. Herber ; Heinz Gornitzka
- 刊名：Organometallics
- 出版年：2016
- 出版时间：February 8, 2016
- 年：2016
- 卷：35
- 期：3
- 页码：346-356
- 全文大小：514K
- ISSN：1520-6041
文摘
Pyramidane and its derivatives are among the most desirable synthetic chemistry targets, whose appealing square-pyramidal design, fascinating nonclassical structure, and unusual bonding features have attracted the permanently growing interest of organic chemists for decades. Although they have been comprehensively approached on theoretical grounds, no member of the pyramidane family was experimentally realized until very recently, thus remaining one of the biggest synthetic challenges for experimental pursuits. In this paper, we report on a series of stable hybrid pyramidanes of group 14 elements, featuring germanium, tin, or lead at the apex of the square pyramid, capping the four-membered-ring base made of carbon, silicon, or germanium atoms. On the basis of the experimental results (X-ray diffraction and NMR and M?ssbauer spectroscopy) and computational studies at the B3LYP/Def2TZVP level of theory (MO, NBO, NRT, and AIM), an extraordinarily high degree of ionicity of the pyramidal apex-to-base bonds was attributed to the overall structure of these nonclassical covalent compounds.