Coordination chemistry at carbon
Coordination chemistry at carbon
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DOI：
10.1038/nchem.248
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发表时间：
2009-07-01
期刊：
影响因子：
21.8
通讯作者：
Fuerstner, Alois
中科院分区：
文献类型：
--
作者：
Alcarazo, Manuel;Lehmann, Christian W.;Fuerstner, Alois
富电子联烯和杂累积烯通常用有机化学的常规符号来描述。以下从发表的结果和最近的计算研究，我们在这里提出了一个主机的晶体学和反应性数据，以及理论结果，这表明在这个系列的许多成员的高度非正则键合的情况。这些实际上必须被解释为配位化合物，其中碳作为“中心原子”，通过供体-受体键与其“配体球”相互作用，即使这些内部配体本身是碳基的。这种捕获性描述并不局限于假定包含碳（o）中心的化合物，碳（o）中心是一种特殊的氧化态，可以通过孪晶变性进行实验探测。由于现有的数据表明，这种对C-C和C-X键的非传统解释比以前预期的更普遍适用，它可能会影响我们对有机化学的理解。
Electron-rich allenes and heterocumulenes are commonly described by the regular notations of organic chemistry. Following on from published results and recent computational studies, we present here a host of crystallographic and reactivity data, as well as theoretical results, that indicate a highly non-canonical bonding situation in many members of this series. These must actually be interpreted as coordination compounds, in which carbon serves as a 'central atom' that interacts with its 'ligand sphere' via donor-acceptor bonds, even if these internal ligands themselves are carbon based. This captodative description is not limited to compounds that supposedly comprise a carbon(o) centre, a peculiar oxidation state that can be probed experimentally by geminal diauration. As the available data suggest that this unconventional interpretation of C-C and C-X bonds is more generally applicable than previously anticipated, it may well affect our understanding of organic chemistry in general.