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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Azines as Electron-Pair Donors to CO2 for N center dot center dot center dot C Tetrel Bonds
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Azines as Electron-Pair Donors to CO2 for N center dot center dot center dot C Tetrel Bonds

机译：Azines作为CO2的电子对供体为N中心点中心点中心点C Tetrel Colds

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摘要

Ab initio MP2/aug'-cc-pVTZ calculations were performed to investigate tetrel-bonded complexes formed between CO2 and the aromatic bases pyridine, the diazines, triazines, tetrazines, and pentazine. Of the 23 unique equilibrium azine:CO2 complexes, 14 have planar structures in which a single nitrogen atom is an electron-pair donor to the carbon of the CO2 molecule, and 9 have perpendicular structures in which two adjacent nitrogen atoms donate electrons to CO2, with bond formation occurring along an N-N bond. The binding energies of these complexes vary from 13 to 20 kJ mol(-1) and decrease as the number of nitrogen atoms in the ring increases. For a given base, planar structures have larger binding energies than perpendicular structures. The binding energies of the planar complexes also tend to increase as the distance across the tetrel bond decreases. Charge transfer in the planar pyridine:CO2 complex occurs from the N lone pair to a virtual nonbonding orbital of the CO, carbon atom. In the remaining planar complexes, charge transfer occurs from an N lone pair to the remote in-plane pi*C-O orbital. In perpendicular complexes, charge transfer occurs from an N-N bond to the adjacent pi*O-C-O orbital of CO2. Decreases in the bending frequency of the CO2 molecule and in the C-13 chemical shielding of the C atom of CO2 upon complex formation are larger in planar structures compared to perpendicular structures. EOM-CCSD spin-spin coupling constants (1t)J(N-C) for complexes with planar structures are very small but still correlate with the N-C distance across the tetrel bond.
机译：进行AB InitiOm2 / Aug'-CC-PVTZ计算以研究CO 2和芳族碱基，二聚胺，三嗪，四嗪和五嗪之间形成的四键键合复合物。在23个独特的均衡氮杂氮：CO 2络合物中，14具有平面结构，其中单个氮原子是CO 2分子的碳的电子对供体，并且9具有垂直结构，其中两个相邻的氮原子将电子捐给CO2，沿NN键发生键形成。这些配合物的结合能量在13至20kJ摩尔（-1）之间变化，并且随着环中的氮原子的数量增加而降低。对于给定基座，平面结构具有比垂直结构更大的粘合能量。由于跨越琴键的距离减小，平面复合物的结合能量也倾向于增加。在平面吡啶中的电荷转移：CO 2复合物从N单床对碳原子的虚拟非粘结轨道发生。在剩余的平面复合物中，电荷转移从N个单位对发生到遥控器内PI * C-O轨道。在垂直复合物中，电荷转移从N-N键与CO 2的相邻PI * O-C-O轨道发生。与垂直结构相比，C-13在C-13的C-13中的C-13化学屏蔽中的C-13化学屏蔽在平面结构上较大。用于平面结构的配合物的EOM-CCSD自旋旋转耦合常数（1T）J（N-C）非常小，但仍然与横跨平板键的N-C距离相关。

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