当前位置：
X-MOL 学术
›
Eur. J. Inorg. Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Agostic Hydrogens in 1‐Norbornyl Metal Cyclopentadienyl Structures
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-09-28 , DOI: 10.1002/ejic.202000714 Zhixiang Fan 1 , Yuchen Hu 1 , Huidong Li 1, 2 , Jia Fu 1 , Qunchao Fan 1 , R. Bruce King 2 , Henry F. Schaefer 2
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-09-28 , DOI: 10.1002/ejic.202000714 Zhixiang Fan 1 , Yuchen Hu 1 , Huidong Li 1, 2 , Jia Fu 1 , Qunchao Fan 1 , R. Bruce King 2 , Henry F. Schaefer 2
Affiliation
|
The first‐row transition metal 1‐norbornyl derivatives CpM(nor) Cp = η5‐C5H5; nor = 1‐norbornyl; M = Ti to Cu), including the experimentally known CpNi(nor) reported by Lehmkuhl and Dimitrov, have been examined by density functional theory and benchmarked by the more accurate DLPNO‐CCSD(T) method. The lowest energy CpM(nor) structures for the later first row transition metals from manganese to copper are found to be high‐spin state structures in which the 1‐norbornyl ligand is bonded to the metal only through the M–C σ‐bond to the bridgehead carbon atom. The favored spin states range from doublet for CpCu(nor) to sextet for CpMn(nor). The pattern of favorable structure types changes for the CpM(nor) derivatives of the earlier first row transition metals to the left of manganese since all of their low energy structures have singly or doubly agostic 1‐norbornyl groups. The agostic C–H–M interactions in the CpM(nor) derivatives are characterized by their reduced density gradients and low ν(C–H) frequencies.
中文翻译：
1-去甲基降冰片烯金属环戊二烯基结构中的氢
所述第一行过渡金属1-降冰片基衍生物CPM（NOR）的Cp =η 5 -C 5 H ^ 5; 也= 1-降冰片烯; M = Ti to Cu），包括Lehmkuhl和Dimitrov报告的实验已知的CpNi（nor），已通过密度泛函理论进行了检验，并通过更精确的DLPNO-CCSD（T）方法进行了基准测试。发现从锰到铜的第一行过渡金属的最低能量CpM（nor）结构是高自旋态结构，其中1-降冰片烯配体仅通过M–Cσ键与金属键合桥头碳原子。有利的自旋态范围从CpCu（nor）的双峰到CpMn（nor）的六重峰。锰左侧的较早第一排过渡金属的CpM（nor）衍生物的有利结构类型模式发生了变化，因为它们的所有低能结构均具有单个或双原子的1-norbornyl基。
更新日期：2020-11-23
中文翻译：
1-去甲基降冰片烯金属环戊二烯基结构中的氢
所述第一行过渡金属1-降冰片基衍生物CPM（NOR）的Cp =η 5 -C 5 H ^ 5; 也= 1-降冰片烯; M = Ti to Cu），包括Lehmkuhl和Dimitrov报告的实验已知的CpNi（nor），已通过密度泛函理论进行了检验，并通过更精确的DLPNO-CCSD（T）方法进行了基准测试。发现从锰到铜的第一行过渡金属的最低能量CpM（nor）结构是高自旋态结构，其中1-降冰片烯配体仅通过M–Cσ键与金属键合桥头碳原子。有利的自旋态范围从CpCu（nor）的双峰到CpMn（nor）的六重峰。锰左侧的较早第一排过渡金属的CpM（nor）衍生物的有利结构类型模式发生了变化，因为它们的所有低能结构均具有单个或双原子的1-norbornyl基。
京公网安备 11010802027423号