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Substituent effects of fused Hammick germylenes: Estimating the stability and reactivity using density functional theory
Journal of Physical Organic Chemistry ( IF 1.8 ) Pub Date : 2021-07-12 , DOI: 10.1002/poc.4262
Marischa Elveny 1 , Nour Abd Alrazzak 2 , Aseel M. Aljeboree 2 , Ayad F. Alkaim 2 , Abdol Ghaffar Ebadi 3
Affiliation  

In this theoretical survey, we compared and contrasted the substituent influences on stability, aromaticity, band gap, atomic charge distribution, and reactivity of 54 singlet and triplet fused Hammick germylenes derived from germabenzopyridine-4-ylidene as well as the synthesized five- and six-membered ones by Herrmann and Driess, respectively. Investigations show (1) the lowest and the highest singlet–triplet energy difference (ΔΕs–t) is demonstrated by fusion of two phosphole rings and two furan rings in ortho-positions (35.6 and 253.6 kJ/mol, respectively) compared with those of the synthesized germylenes (208.8 and 179.9 kJ/mol, respectively). (2) Whereas fusion of benzene, pyridine, phosphinine, and phosphole rings thermodynamically destabilizes the corresponding germylenes, fusion of pyrrole, furan, and thiophene rings stabilizes the corresponding germylenes. (3) The tendency of substituent influences in number and size of rings is arranged by two five-membered rings > one five-membered rings > one six-membered rings > two six-membered rings. (4) While pyrrole, furan, and thiophene rings kinetically stabilize the corresponding germylenes, other rings destabilize their germylenes with respect to germapyridine-4-ylidene and the isolated germylene's Driess. (5) All singlet Hammick germylenes reveal lower nucleophilicity and softness, also higher electrophilicity, chemical potential, and global hardness than their scrutinized triplet states. (6) We are waiting for experimental testing and verifications to fuse heterocyclic rings to the germapyridine-4-ylidene's plane in a favorable spatial position to act not only as π-electron giver but also σ-electron receiver.

中文翻译:

融合 Hammick 锗烯的取代基效应:使用密度泛函理论估计稳定性和反应性

在这项理论调查中,我们比较和对比了取代基对稳定性、芳香性、带隙、原子电荷分布和反应性的影响,54 个单线态和三线态稠合的 Hammick 亚锗烯以及合成的 5-和 6 -分别是 Herrmann 和 Driess 的成员。研究表明 (1) 最低和最高的单线态-三线态能量差 (Δ Ε s-t ) 是通过两个磷环和两个呋喃环在邻位的融合来证明的。位(分别为 35.6 和 253.6 kJ/mol)与合成的亚锗烯(分别为 208.8 和 179.9 kJ/mol)相比。(2) 苯、吡啶、膦和磷环的融合在热力学上使相应的锗烯不稳定,而吡咯、呋喃和噻吩环的融合使相应的锗烯稳定。(3)取代基对环数和环大小的影响趋势为2个五元环>1个五元环>1个六元环>2个六元环。(4) 虽然吡咯、呋喃和噻吩环在动力学上稳定相应的亚锗烯,但其他环使它们的亚锗烯相对于 germapyridine-4-ylidene 和分离的亚锗烯的 Driess 不稳定。(5) 所有单线态 Hammick 锗烯都显示出较低的亲核性和柔软度,还比其仔细检查的三重态具有更高的亲电性、化学势和整体硬度。(6) 我们正在等待实验测试和验证,以在有利的空间位置将杂环融合到锗吡啶-4-亚基平面上,不仅可以作为π -电子给予者和σ-电子接受者。
更新日期:2021-07-12
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