本文選題：硅烯 + 類硅烯　； 參考：《煙臺大學(xué)》2017年碩士論文

【摘要】：本論文主要研究了若干三重態(tài)硅烯和類硅烯的結(jié)構(gòu)、性質(zhì)和反應(yīng)。1.采用M06-2X和QCISD方法研究了若干新型含氮雜環(huán)卡賓單元的硅烯,計(jì)算了它們的單重態(tài)及三重態(tài)的結(jié)構(gòu)和能量。結(jié)果表明,這些硅烯的三重態(tài)能量比單重態(tài)能量低,基態(tài)為三重態(tài),引進(jìn)氮雜環(huán)卡賓骨架能夠提高三重態(tài)硅烯的穩(wěn)定性。2.采用M06-2X和QCISD方法研究了若干新型含氮雜環(huán)卡賓單元的類硅烯,計(jì)算了它們的單重態(tài)及三重態(tài)的結(jié)構(gòu)和能量。結(jié)果表明,這些類硅烯的三重態(tài)能量比單重態(tài)能量要低,基態(tài)為三重態(tài),引進(jìn)的氮雜環(huán)卡賓骨架可以提高三重態(tài)類硅烯的穩(wěn)定性。同時(shí)研究了某些三重態(tài)類硅烯與NH_3和H_2O的插入反應(yīng)。3.采用M06-2X和QCISD方法對三重態(tài)類硅烯RB=SiLiF(R=CH_3,C_2H_5)在氣相中與HF,H_2O和NH_3的插入反應(yīng)進(jìn)行了研究。計(jì)算結(jié)果表明,在插入反應(yīng)過程中,勢能面上存在著一個(gè)三元環(huán)結(jié)構(gòu)R-Si-H(R=F,OH,NH_2)的過渡態(tài)(TS)和一個(gè)中間體(IM)連接反應(yīng)物和產(chǎn)物。RB=SiLiF(R=CH_3,C_2H_5)與RH(R=F,OH,NH_2)發(fā)生插入反應(yīng)的機(jī)理相同,但反應(yīng)活性順序并不相同,在相同反應(yīng)條件下反應(yīng)活性順序都是H—FH—OHH—NH_2。4.采用M06-2X和QCISD方法對類硅烯H_2SiAlCl_3與RH(R=F,OH,NH_2,Cl,SH,PH_2)在氣相和溶劑中的取代反應(yīng)進(jìn)行研究。計(jì)算結(jié)果表明,RH分子可以從兩種不同的位置進(jìn)攻H_2SiAlCl_3分子,從而進(jìn)一步發(fā)生取代反應(yīng)。而且,當(dāng)RH分子從Si-Al鍵的上方進(jìn)攻時(shí),取代反應(yīng)更加容易發(fā)生。溶劑化效應(yīng)結(jié)果表明,溶劑的存在不利于取代反應(yīng)的進(jìn)行。
[Abstract]:In this paper, the structure, properties and reaction of triplet silicene and silylidene are studied. The structure and energy of some new nitrogen-containing heterocyclic carbene units have been studied by M06-2X and QCISD methods. The structure and energy of their singlet and triplet states have been calculated. The results show that the triplet energy of these silicene is lower than that of single state, and the ground state is triplet state. The introduction of carbene skeleton of nitrogen heterocyclic can improve the stability of triplet silicene. By using M06-2X and QCISD methods, the structure and energy of some new nitrogen-containing heterocyclic carbene units are studied. The structure and energy of their singlet and triplet states are calculated. The results show that the triplet energy of these silicene is lower than that of the single state, and the ground state is triplet. The introduction of the carbene skeleton of nitrogen heterocyclic can improve the stability of triplet silicene. At the same time, the insertion reactions of some triplet silicene with NH _ 3 and H _ 2O were studied. M06-2X and QCISD methods were used to study the intercalation reaction of triplet silicene RBSiLiFU RCH3 / C _ 2H _ 5) with HFH _ 2O and NH _ 3 in the gas phase. The calculated results show that during the insertion reaction, there is a transition state (TSTS) and an intermediate (IMM) of a ternary ring structure R-Si-Hn / RFN / NH _ (2) on the potential energy surface. The mechanism of the insertion reaction is the same as that of the RHRRFU / OHH _ (2) / RHRRRFU / OFO _ (NH _ 2) / RHRRRFU / OFO _ (NH _ 2) / RHRRRFU / OFU / NH _ 2) during the intercalation reaction. But the order of reaction activity is not the same. Under the same reaction conditions, the order of reaction activity is H-FH-OHH-NH2.4. M06-2X and QCISD methods were used to study the substitution reactions of 2SiAlCl _ 3 and RHH ~ (+) / R ~ (H ~ (+) ~ (FU) ~ (NH _ (2) / H _ (H _ (H) ~ (NH _ (2) / H _ (H) ~ (2) in the gaseous phase and solvent. The results show that the RH molecule can attack Hs _ 2SiAlCl _ 3 molecule from two different positions, thus the substitution reaction will occur further. Moreover, when RH molecules attack from the top of Si-Al bond, substitution reaction occurs more easily. The solvation effect shows that the existence of solvent is unfavorable to the substitution reaction.
【學(xué)位授予單位】：煙臺大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O627.41

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