本研究利用量子計算和NBO分析來研究Z-Ti[-Y(CH2)2-]3N和Z-V[-Y(CH2)2-]3N等化合物的結構及電子組態，其中Z≡F、Cl、Br、I、OH、NH2、CH3，Y≡O、S、CH2、NCH3。在本研究過程當中，發現所有的Z-Ti[-Y(CH2)2-]3N和Z-V[-Y(CH2)2-]3N化合物之中，Z…Ti…N和Z…V…N之間具有三中心四電子(3c-4e)鍵結，而且N原子以孤對電子與中心金屬Ti或V做配位鍵結。Z-V〔-NCH3(CH2)2-〕3N的三中心四電子特性比Z-Ti〔-NCH3(CH2)2-〕3N來得明顯，而在不同的Y官能基下Lp N → σ*VZ的E(2)數值大小趨勢：Y≡S＞Y≡NCH3≧Y≡CH2＞Y≡O。Y官能基是決定Ti…N和V…N之間的核間作用力大小的主要因素，在比較N原子與Ti-Z、V-Z之間的作用力時，發現Y≡CH2時，作用力最好，Y≡O時，作用力最差。在伸縮位能比較方面，根據F-Ti(-YCH2CH2-)3N與F-V(-YCH2CH2-)3N兩者相比結果，前者的電子總能變化反應出其分子結構不容易有大幅度的改變。在F-Ti(-YCH2CH2-)3N與F-V(-YCH2CH2-)3N的伸縮位能曲線圖裡，發現當Y≡NCH3時，會有兩種異構物出現，其中以〝axial〞結構最為穩定。

　The structures and electronic configurations of Z-Ti[-Y(CH2)2-]3N and Z-V[-Y(CH2)2-]3N are investigated by quantum calculations and NBO analysis, where Z≡F, Cl, Br, I, OH, NH2, and CH3, Y≡O, S, CH2, and NCH3. The Z…Ti…N of the Z-Ti[-Y(CH2)2-]3N and the Z…V…N of the Z-V[-Y(CH2)2-]3N are characterized by three center-four electron (3c-4e) bonding, and the bonding is mainly a dative contribution from the nitrogen lone pair for three center bonding. 3c-4e bonding is less significant in the Z-Ti[-Y(CH2)2-]3N than it is in the Z-V[-Y(CH2)2-]3N, and the energy of the orbital interaction nN → *VZ decreases in the order Y≡S＞Y≡NCH3≧Y≡CH2＞Y≡O when the Y group is changed. The results of calculations predict that the interaction between the nitrogen atom and the Ti-Z moiety or V-Z moiety is the strongest for the cases of Y≡CH2 and the weakest in the other cases of Y≡O. Comparison of stretching potential for Z-Ti[-Y(CH2)2-]3N and Z-V[-Y(CH2)2-]3N, we expect that the former structures are difficult to change. Besides, there are two isomers in the cases of Y≡NCH3 and the 〝axial〞isomer is more stable.

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