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反夹心化合物E-C5-nH5-nNn-E+和E-C5-nH5-nPn-E+(n=1,2,3; E=Al,Ga,In,Tl)的理论研究

Theoretical Study on Inverse Sandwich Complexes E-C5-nH5-nNn-E+ and E-C5-nH5-nPn-E+ (n=1, 2, 3; E=Al, Ga, In, Tl)

  • 摘要: 研究了含有低价族元素的反夹心化合物E-C5-nH5-nNn-E+和E-C5-nH5-nPn-E+(n=1,2,3; E=Al,Ga,In,Tl).(η5, η5) 配位的反夹心构型E-C5-nH5-nNn-E+ 在能量上不稳定或不存在.而(η5,η5)配位的反夹心构型E-C5-nH5-nPn-E+不但在能量上稳定, 在解离过程中也具有稳定性. 对于含有相同的E元素来说,E-C5-nH5-nPn-E+的解离稳定性随着n的增加而降低;而对于确定的n来说, 含有不同E的化合物的解离能是类似的.其中E-C4H4P-E+的解离稳定性与已知的E-C5H5-E+非常相似.C5-nH5-nPn与E之间的相互作用主要是离子性的. 由于在(η5,η5)配位的E-C5-nH5-nNn-E+中,E和P原子上都具有孤对电子,因此该反夹心化合物可以作为多电子供体.

     

    Abstract: The inverse sandwiches E-C5-nH5-nNn-E+ and E-C5-nH5-nPn-E+ (n=1, 2, 3; E=Al, Ga, In, Tl) with low-valent boron group elements are studied. The (η5,η5) coordinated inverse sandwich E-C5-nH5-nNn-E+ is unstable in energy or nonexistent. However, the (η5,η5) coordinated E-C5-nH5-nPn-E+ is not only stable in energy, but also stable against dissociation. The dissoction stability E-C5-nH5-nPn-E+ with the same E element decreases as the number n increases, while for the certain n number, the dissociation energies with different E elements are close to each other. E-C4H4P-E+ has similar dissocition stability to the well-known E-C5H5-E+. The inteaction between C5-nH5-nPn and lowvalent E element is mainly ionic. Since lone pairs of electrons locate on both E and P atoms, the (η5, η5) coordinated inverse sandwich E-C5-nH5-nPn-E+ would act as multi electron-donors.

     

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