Theoretical study on interactions of N-heterocyclic carbene with the bare first-row transition metals
Theoretical study on interactions of N-heterocyclic carbene with the bare first-row transition metals
复制标题
N-杂环卡宾与裸露的第一排过渡金属相互作用的理论研究
DOI：
10.1007/s00214-016-1922-9
复制
发表时间：
2016-06
影响因子：
1.7
通讯作者：
Cao, Ze-Xing
中科院分区：
文献类型：
--
作者：
Zhang, Xiang-Fei;Sun, Ming-Jun;Cao, Ze-Xing
从理论上探讨了自由和取代的N-杂环卡宾（NHC）及其与裸第一行过渡金属（TM）配合物的电子和结构特征。结果表明，NHC的给电子行为可以通过引入取代基来调节，NHC与TM的σ-成键作用强烈依赖于TM的d-电子构型. B3 LYP和CCSD（T）预测的键离解能呈现双峰分布，最大值分别出现在[NHC-V]（26.2 kcal/mol）和[NHC-Ni]（29.7 kcal/mol）中，在接受NHC的σ孤对后，分别具有稳定的半满和满满构型.利用B3 LYP-D3方法，从TM与NHC中C=C双键的π相互作用出发，对[NHC-TM]的η2型结构进行了理论计算.对于d <10的Zn，没有发现σ-型结构，所有的几何优化尝试都收敛到仅为η6-型结构，这是由于弱的芳香π相互作用引起的.对于其它的TM，它们的η2型结构是由TM与C=C双键之间的π相互作用决定的。σ-和π-型[NHC-TM]复合物可以容纳额外的NHC配体形成稳定的[NHC-TM-NHC]，并且对于大多数裸TM，第二个NHC的引入可以增强TM和NHC之间的成键作用，显示了多个NHC配体对TM-NHC成键的协同作用。
The electronic and structural features of the free and substituted N-heterocyclic carbenes (NHCs) and their complexes with the bare first-row transition metals (TMs) have been explored theoretically. The present results indicate that the electron-donating behavior of NHC can be tuned by introduction of the substituent, and the NHC–TM σ-bonding interactions strongly depend on the d-electron configuration of TMs. The B3LYP- and CCSD(T)-predicted bond dissociation energies show a double-peak profile, and the maxima appear in [NHC–V] (26.2 kcal/mol) and [NHC–Ni] (29.7 kcal/mol) with the stable half- and full-filleddconfigurations, respectively, after accepting the σ-lone pair of NHC. Theoretical calculations on the η2-type structure of [NHC–TM] from π interactions between TM and C=C double bond in NHC are also done by B3LYP-D3. For Zn withd10, no σ-type structure was located, and all geometry optimization attempts converge to only metastable η6-type configuration, arising from the weak aromatic π interactions. For other TMs, the π interactions between the double C=C bond and TM are responsible for their η2-type structures. The σ- and π-type [NHC–TM] complexes can accommodate additional NHC ligand to form stable [NHC–TM–NHC], and the introduction of second NHC can enhance the bonding interactions between TM and NHCs for most of the bare TMs, showing cooperation effect of the multiple NHC ligands on the TM–NHC bonding.
登录
查看更多内容
影响因子：
2.8
作者：
M. Cheng;Ching‐Han Hu
通讯作者：
M. Cheng;Ching‐Han Hu
影响因子：
4.4
作者：
HAY, PJ;WADT, WR
通讯作者：
WADT, WR
DOI：
10.1021/j100010a013
发表时间：
1995
期刊：
The Journal of Physical Chemistry
影响因子：
--
作者：
K. Hoshino;T. Kurikawa;H. Takeda;A. Nakajima;K. Kaya
通讯作者：
K. Hoshino;T. Kurikawa;H. Takeda;A. Nakajima;K. Kaya
影响因子：
2.8
作者：
RAGHAVACHARI, K;TRUCKS, GW;HEADGORDON, M
通讯作者：
HEADGORDON, M
影响因子：
2.9
作者：
K. Miyajima;Kazuhiko Muraoka;M. Hashimoto;Tomokazu Yasuike;S. Yabushita;A. Nakajima;K. Kaya
通讯作者：
K. Miyajima;Kazuhiko Muraoka;M. Hashimoto;Tomokazu Yasuike;S. Yabushita;A. Nakajima;K. Kaya