• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemistry: A European journal >Carbodicarbenes and related divalent carbon(0) compounds
【24h】

Carbodicarbenes and related divalent carbon(0) compounds

机译：碳二烯和相关的二价碳（0）化合物

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Quantum-chemical calculations using DFT and ab initio methods have been carried out for fourteen divalent carbon(0) compounds (carbones), in which the bonding situation at the two-coordinate carbon atom can be described in terms of donor-acceptor interactions L→C←L. The chargeand energy-decomposition analysis of the electronic structure of compounds 1-10 reveals divalent carbon(0) character in different degrees for all molecules. Carbone-type bonding L→C←L is particularly strong for the carbodicarbenes 1 and 2, for the "bent allenes" 3a, 3b, 4a, and 4b, and for the carbocarbenephosphoranes 7a, 7b, and 7c. The last-named molecules have very large first and large second proton affinities. They also bind two BH _3 ligands with very high bond energies, which are large enough that the bis-adducts should be isolable in a condensed phase. The second proton affinities of the complexes 5, 6, and 8-10 bearing CO or N_2 as ligand are significantly lower than those of the other molecules. However, they give stable complexes with two BH_3 ligands and thus are twofold Lewis bases. The calculated data thus identify 1-10 as carbones L→C←L in which the carbon atom has two electron pairs. The chemistry of carbones is different from that of carbenes because divalent carbon(0) compounds CL _2 are π donors and thus may serve as double Lewis bases, while divalent carbon(II) compounds are p acceptors. The theoretical results point toward new directions for experimental research in the field of low-coordinate carbon compounds.
机译：使用DFT和从头算方法对14个二价碳（0）化合物（碳）进行了量子化学计算，其中两个配位碳原子的键合情况可以根据供体-受体相互作用描述L→ C←L。化合物1-10的电子结构的电荷和能量分解分析显示，所有分子在不同程度上具有二价碳（0）特征。碳型键L→C←L对于碳二碳烯1和2，“弯曲的烯” 3a，3b，4a和4b以及碳碳烯基膦酸酯7a，7b和7c特别强。姓氏分子具有很大的第一和第二质子亲和力。它们还以非常高的键能结合两个BH _3配体，它们的大小足够大，以至于双加合物在缩合相中应该是可分离的。带有CO或N_2作为配体的配合物5、6和8-10的第二质子亲和力明显低于其他分子。但是，它们可与两个BH_3配体形成稳定的络合物，因此是两倍的Lewis碱。因此，计算出的数据确定1-10个碳为L→C←L，其中碳原子具有两个电子对。碳的化学与碳烯的化学不同，因为二价碳（0）化合物CL _2是π供体，因此可以用作双路易斯碱，而二价碳（II）化合物是p受体。理论结果为低配位碳化合物领域的实验研究指明了新的方向。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号