几类多重键化合物的结构与反应机理的理论研究
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摘要
本文利用量子化学计算方法预测了一类新的三键化合物XCNN (X=Ge, Sn, Pb),揭示了Ge2+N2双分子反应以及腈炔交叉置换反应(NACM)的反应机理。主要内容如下:
i)利用CCSD(T)//B3LYP方法对[XCN2] (X=Ge, Sn, Pb)系列分子各个异构体的热力学和动力学稳定性进行了研究。发现XCNN是一个含有XC三键的异构体,稳定性非常好,有利于实验室探测与合成。我们的研究为将来该类新型三键化合物的合成提供了一种新思路。
ii)利用CCSD(T)和B3LYP方法研究了Ge2和N2双分子反应的反应机理。IRC路径计算表明,文献所阐述的单重态反应机理是不正确的,正确的反应主通道为:3Ge2+N2 3c-GeNNGe CI 1Ge-cNNGe 1GeNNGe,需要经过一个三态-单态的圆锥交叉点CI。我们的结果很好地解释了文献报道的低温激光溅射实验,并为类似双分子反应如Si2/Sn2+N2的机理研究提供了参考。
iii)在DFT方法下对NACM反应机理进行了理论研究。结果显示该反应遵循四元环机理,即通过不稳定的四元环异构体生成产物,与近期的实验现象吻合。计算结果有望为杂原子参与的新型多重键置换反应的设计提供了参考。
In this thesis, the structures and stability of [XCN2] molecules (X=Ge, Sn, Pb), reaction mechanisms of Ge2 with N2, and catalytic nitrile-alkyne cross-metathesis (NACM) have been investigated by means of the quantum chemical methods. The thermodynamical and kinetic stability of various [XCN2] isomers, singlet and triplet pathways as well as the singlet-triplet tunneling of the Ge2+N2 reaction, and two main evolution channels of the NACM reaction have been provided. The calculation results agree well with available experiments. The results of this thesis may provide useful information for the further theoretical and experimental studies on related systems. The main results are summarized as follows:
1. The CCSD(T)//B3LYP method was applied to study the structures and energetics of various isomers and transition states on the [XCN2] potential energy surface. Five linear forms XNCN, XCNN, XNNC, NXCN, NXNC and two cyclic forms X-cCNN and X-cNCN were located as energy minima. The results showed that linear isomers XNCN, XCNN and XNNC each possess good kinetic stability, and thus are promising for laboratory characterization. The molecular orbital, hydrogenation heat and bond dissociation energy analysis all indicated that XCNN is associated with a XC triple bond. Moreover, XCNN is the most stable isomer after XNCN in both thermodynamics and kinetics. Our designed triply bonded molecules differ from the traditional alkynes and belong to a novel type. Taking GeCNN as an example, we proposed that the transiton metal carbonyl coordination can provide considerable stabilization to the designed XCNN structure for the sake of laboratory detection. Our computational work might provide new insights for future study of the XC triply bonded molecules.
2. The CCSD(T)//B3LYP method was used to study the reaction of Ge2 with N2. A“singlet-triplet intersection mechanism”was disclosed. The starting reagent, triplet Ge2, initially reacts with the environmental gas N2 to form a triplet four-membered ring intermediate 3c-GeGeNN, which would undergo a singlet-triplet canonical intersection (CI) point to form a three-membered ring isomer 1Ge-cNNGe. Isomer 1Ge-cNNGe will further undergo a ring-opening to generate the singlet isomer 1GeNNGe as the enventual product. Thus, the main reaction channel can be written as: 3Ge2+N2 3c-GeNNGe CI 1Ge-cNNGe 1GeNNGe. Our computational results can reasonably explain the recent low temperature laser ablation experiment. By contrast, the careful IRC analysis showed that the two transiton states previously located are erroneously connected. Therefore, the previously proposed mechanism via a singlet reaction pathway (“singlet mechanism”) to form the singlet GeNNGe is incorrect. The present results could provide useful information for future mechanistic studies on the analogous bimolecular reactions such as Si2/Sn2+N2.
3. The catalytic nitrile-alkyne cross-metathesis (NACM) was studied by meansof the DFT method. A four-membered ring (4MR) mechanism was revealed, i.e., a ring-closure process is initially proceeded to form a 4MR intermediate that can easily undergo the bond-rearrangement to form another 4MR intermediate, which would take ring-opening to generate the eventual products. The two 4MR intermediates are kinetically unstable and have little likelihood to be observed in laboratory. In addition, since the rate-determining step (ring-closure) needs to overcome high barriers, the overall reaction should be slow. The main reaction channel is: R: [W]N+CH3CCCH3?IM1?IM2?[W]CCH3+CH3CN [W]=(CH3O)3W.
In principle, the NACM reaction should coexist with the AM reaction in experiments, and the former can provide necessary reagents for the latter. NACM is associated with high barrier and low speed, while AM is associated with relatively low barrier and high speed. Moreover, one drawback of the AM reaction is that when the concentration of reagent is high, the alkynes and (RO)3W≡CR′would polymerize to deactive the WC triply bonded catalysis. Thus, the NACM controls the concentration of AM, which will lower the happening possibility of side reactions of AM. As a result, the overall reaction yield is raised. Our results are consistent with the observed experimental phenomena and couldbe helpful for future design of more effective catalysts.
i)利用CCSD(T)//B3LYP方法对[XCN2] (X=Ge, Sn, Pb)系列分子各个异构体的热力学和动力学稳定性进行了研究。发现XCNN是一个含有XC三键的异构体,稳定性非常好,有利于实验室探测与合成。我们的研究为将来该类新型三键化合物的合成提供了一种新思路。
ii)利用CCSD(T)和B3LYP方法研究了Ge2和N2双分子反应的反应机理。IRC路径计算表明,文献所阐述的单重态反应机理是不正确的,正确的反应主通道为:3Ge2+N2 3c-GeNNGe CI 1Ge-cNNGe 1GeNNGe,需要经过一个三态-单态的圆锥交叉点CI。我们的结果很好地解释了文献报道的低温激光溅射实验,并为类似双分子反应如Si2/Sn2+N2的机理研究提供了参考。
iii)在DFT方法下对NACM反应机理进行了理论研究。结果显示该反应遵循四元环机理,即通过不稳定的四元环异构体生成产物,与近期的实验现象吻合。计算结果有望为杂原子参与的新型多重键置换反应的设计提供了参考。
In this thesis, the structures and stability of [XCN2] molecules (X=Ge, Sn, Pb), reaction mechanisms of Ge2 with N2, and catalytic nitrile-alkyne cross-metathesis (NACM) have been investigated by means of the quantum chemical methods. The thermodynamical and kinetic stability of various [XCN2] isomers, singlet and triplet pathways as well as the singlet-triplet tunneling of the Ge2+N2 reaction, and two main evolution channels of the NACM reaction have been provided. The calculation results agree well with available experiments. The results of this thesis may provide useful information for the further theoretical and experimental studies on related systems. The main results are summarized as follows:
1. The CCSD(T)//B3LYP method was applied to study the structures and energetics of various isomers and transition states on the [XCN2] potential energy surface. Five linear forms XNCN, XCNN, XNNC, NXCN, NXNC and two cyclic forms X-cCNN and X-cNCN were located as energy minima. The results showed that linear isomers XNCN, XCNN and XNNC each possess good kinetic stability, and thus are promising for laboratory characterization. The molecular orbital, hydrogenation heat and bond dissociation energy analysis all indicated that XCNN is associated with a XC triple bond. Moreover, XCNN is the most stable isomer after XNCN in both thermodynamics and kinetics. Our designed triply bonded molecules differ from the traditional alkynes and belong to a novel type. Taking GeCNN as an example, we proposed that the transiton metal carbonyl coordination can provide considerable stabilization to the designed XCNN structure for the sake of laboratory detection. Our computational work might provide new insights for future study of the XC triply bonded molecules.
2. The CCSD(T)//B3LYP method was used to study the reaction of Ge2 with N2. A“singlet-triplet intersection mechanism”was disclosed. The starting reagent, triplet Ge2, initially reacts with the environmental gas N2 to form a triplet four-membered ring intermediate 3c-GeGeNN, which would undergo a singlet-triplet canonical intersection (CI) point to form a three-membered ring isomer 1Ge-cNNGe. Isomer 1Ge-cNNGe will further undergo a ring-opening to generate the singlet isomer 1GeNNGe as the enventual product. Thus, the main reaction channel can be written as: 3Ge2+N2 3c-GeNNGe CI 1Ge-cNNGe 1GeNNGe. Our computational results can reasonably explain the recent low temperature laser ablation experiment. By contrast, the careful IRC analysis showed that the two transiton states previously located are erroneously connected. Therefore, the previously proposed mechanism via a singlet reaction pathway (“singlet mechanism”) to form the singlet GeNNGe is incorrect. The present results could provide useful information for future mechanistic studies on the analogous bimolecular reactions such as Si2/Sn2+N2.
3. The catalytic nitrile-alkyne cross-metathesis (NACM) was studied by meansof the DFT method. A four-membered ring (4MR) mechanism was revealed, i.e., a ring-closure process is initially proceeded to form a 4MR intermediate that can easily undergo the bond-rearrangement to form another 4MR intermediate, which would take ring-opening to generate the eventual products. The two 4MR intermediates are kinetically unstable and have little likelihood to be observed in laboratory. In addition, since the rate-determining step (ring-closure) needs to overcome high barriers, the overall reaction should be slow. The main reaction channel is: R: [W]N+CH3CCCH3?IM1?IM2?[W]CCH3+CH3CN [W]=(CH3O)3W.
In principle, the NACM reaction should coexist with the AM reaction in experiments, and the former can provide necessary reagents for the latter. NACM is associated with high barrier and low speed, while AM is associated with relatively low barrier and high speed. Moreover, one drawback of the AM reaction is that when the concentration of reagent is high, the alkynes and (RO)3W≡CR′would polymerize to deactive the WC triply bonded catalysis. Thus, the NACM controls the concentration of AM, which will lower the happening possibility of side reactions of AM. As a result, the overall reaction yield is raised. Our results are consistent with the observed experimental phenomena and couldbe helpful for future design of more effective catalysts.
引文
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7 Bibal C., Mazieáres S., Gornitzka H., Couret C., A route to a germanium-carbon triple bond: First chemical evidence for a germyne, Angew. Chem. Int. Ed., 2001, 40(5): 952—954
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10 Liao H. Y., Su M. D., Chu S. Y., A stable species with a formal Ge≡C triple bond– a theoretical study, Chem. Phys. Letter., 2001, 341(1-2): 122—128
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17我们这里假定PbC多重键完全分解所需的能量为键解离能,即M1PbCM2→M1Pb+CM2,每个碎片电子态为其基态.具体计算在CCSD(T)/B2//B3LYP/B1方法下进行,其中基组B1为Pb原子使用Lanl2dz基组,其他原子使用6-311+G(2d,2p),基组B2为Pb原子使用CEP-121g基组,其他原子使用6-311++G(3df,2dp)基组
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20 Scheller M. K., Cederbaum L. S., Bonding between C2 and N2: A Localization-InducedσBond, J. Am. Chem. Soc., 1990, 112(26):9484-9490
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17我们这里假定PbC多重键完全分解所需的能量为键解离能,即M1PbCM2→M1Pb+CM2,每个碎片电子态为其基态.具体计算在CCSD(T)/B2//B3LYP/B1方法下进行,其中基组B1为Pb原子使用Lanl2dz基组,其他原子使用6-311+G(2d,2p),基组B2为Pb原子使用CEP-121g基组,其他原子使用6-311++G(3df,2dp)基组
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