燃料化学学报2016，Vol.44Issue(3)：335-341,7.
取代基对木质素三聚体模型化合物醚键均裂反应影响的密度泛函理论研究
Theoretical study on the effects of the substituent groups on the homolysis of the ether bond in lignin trimer model compounds
摘要
Abstract
The homolytic bond dissociation energi es ( BDEs) of Cα-Oa nd Cβ-O bno ds in 27 lignin trimer model compounds were calculated by emplyo ing density functional theory methods at M062 X level with 6-31++G( d,p) basis set;the effcet s of vair ous subsit tune t groups( CH3 , CH2 OH and OCH3 )a t different positions on theB DE s of Cα-O and Cβ-O bonsd were invets igated.The results indicated ht at a sni gle methoxyl group at R2 or R3 has a minor influence on the BDE of Cβ-O bond, whereas two methoxyl groups at R2 and R3 lead to an obvious decrae se in the BDE of Cβ-O bond.The decrement in the BDE of Cβ-O bond fromt he methoxyl groups at R2 and R3 ac n be enah nced byt he mte hoxyl groups ta R4 and R5 , but si hardly influenced by thes ubstituent groups at R1 .Meanwhile, the BDE of Cα-O bond is gradually reduced when the H atoms at R4 and R5 are successively substituted with methoxyl groups; the decrement in the BDE of Cα-O bond from the methoxyl groups at R4 and R5 can be strengthened by the methoxyl groups at R2 and R3 .Furthermore, the methyl and hydroxymethyl groups at R1 can gradually increase the BDE of Cα-O bond and this effect is weakened when the H atoms at R2 and R3 are successively substituted with methoxyl groups.The methyl group at R1 has little influence on the BDE of Cβ-O bond, which is however dramatically increased by the hydroxymethyl group at R1 .关键词
木质素三聚体/取代基/均裂/键解离能/密度泛函理论Key words
lignin trimer model compound/substituent group/homolysis/bond dissociation energy/density functional theory分类
能源科技引用本文复制引用
蒋晓燕,陆强,董晓晨,胡斌,董长青..取代基对木质素三聚体模型化合物醚键均裂反应影响的密度泛函理论研究[J].燃料化学学报,2016,44(3):335-341,7.基金项目
The project was supported by the National Natural Science Foundation of China （51576064） and Fundamental Research Funds for the Central Universities （2014ZD17）．@@@@国家自然科学基金（51576064）和中央高校基本科研业务费（2014ZD17）项目资助 （）
