过渡金属催化偶联反应机理的理论研究-材料学专业论文.docxVIP

日 日 / 进行，并揭示了有效催化作用产生的机制。 ，叫，关键询z 过波金属催化: 偶联反应:反应机理:伽乙瞰基工碗缩烯酣: ，叫， 2ω腆代晒苯; 2-噬炕酣:宿度泛函理论: 活化能: 溶剂效应: Mm Mm J 咖 Theoretical Study on Reaction Mechanism of 协 Coupling Recaction Catalyzed by Transtion Metal It 、嘻 MaJor Materia1s Science Graduate Xintong Su Supervisor Laicai Li Abstract: In pr四ent diss町幅tion， density functiona1也ω叩(DFT) wωusedω study two typiω1 ∞upling r，侃侃ons cata1ysed by 田nsition metal: 由.e C-C ∞lupling reaction of a-acetyl ketendi由ioaceta1s wi也 TiC4-cata1yst and C割 ∞upling reaction of 2-iodo-selenophene wi由2咱xazolidinoneωta1ysd by Cul.The main substan仰s are shown below: The acylation reaction mechanism ofαm血on aωm of α-acetyl ketendi由ioω制制也 TiC4-ωta1yst w;剧创lculated 副伽 B3LYP/6311G* level. The geom础iωof r，剧创削俑， int耐m创iat倒，位ansition 剖at俑， and 伊oduc阳 were 叩timized and verified by m棚ns of vibration 食。quency ana1ysis. The relative reaction withoutω阳lyst w拙 dωinverstiga时伽 ωmparison. The polarizable ∞n伽:uum modelσCM) w拙剧创仙 simulate 伽r reac悦。n pro仰础恤 dichlorome由ane solution. In addition， Nature Bond ω也ita1 (NBO) and AωIms In Molωul臼(AIM)也ωries were usedωdisωS8 bond naturωand orbita1 interactions. The ∞mputa咀ona1 r四u1ts 旭di创始也at 也e activation b缸ri缸 wi也 TiC4-ωta1yst is lower than 也e activation barri缸 wi也.outωta1yst. The rl囚u1ts indiωte 也at 由eTiC4 ωn 伊omote 伽 reaction. The solventωndecrease 也e barriers great1y. 事The mechanism ofωrbon咄trogenωupling reaction of 2-iodo-selenophene wi由 2-oxazolidinone cata1ysd by CuI has b伺n investigated 硝由e B3LYP/6-311G* leve1. Aωita1ysted cycle w础 designed and ca1cu1ated. The geom仰t础。f r阳ctan钮， 旭，termediat邸， tran8ition 创翩翩相d produ创8 were ob蚀ined. Theωlcu1ated results 事 ∞F ∞ 4 indi佣阳也硝也e reaction i8 very mpliωted and prωωs 也rough five steps. The CuI ca组l归t play a bridge role 扭曲eωlupling reaction， which avoid 也ehigh 由咀n 回 IV IV 如阳-memebered 衍ansition 阳te in 伽 directωlupling withoutω阳lyst and result in it procωds 侃sily. ourωlculation results are in gl∞d agreement wi伽伽e fI 饵periment， which prove 也at the transi