期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 8, 页码 3377-3386出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201405416
关键词
carbenes; density functional calculations; donor-acceptor systems; ligands; synthetic methods
资金
- Australian Research Council [DE130100186]
- La Trobe Institute for Molecular Science
- Deutsche Forschungsgemeinschaft
- Australian Research Council [DE130100186] Funding Source: Australian Research Council
The attempted synthesis of NHC-stabilized dicarbon (NHC=C=C=NHC) through deprotonation of a doubly protonated precursor ([NHC-CH=CH-NHC](2+)) is reported. Rather than deprotonation, a clean reduction to NHC=CH-CH=NHC is observed with a variety of bases. The apparent resistance towards deprotonation to the target compound led to a reinvestigation of the electronic structure of NHC -> C=C <- NHC, which showed that the highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) gap is likely too small to allow for isolation of this species. This is in contrast to the recent isolation of the cyclic alkylaminocarbene analogue (cAAC=C=C=cAAC), which has a large HOMO-LUMO gap. A detailed theoretical study illuminates the differences in electronic structures between these molecules, highlighting another case of the potential advantages of using cAAC rather than NHC as a ligand. The bonding analysis suggests that the dicarbon compounds are well represented in terms of donor-acceptor interactions L -> C-2 -> L (L=NHC, cAAC).
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据