New insights into the insertion reactions of germylenoid H2GeLiF with RH (R = F, OH, NH2).
J Mol Model
; 21(4): 68, 2015 Apr.
Article
em En
| MEDLINE
| ID: mdl-25750023
ABSTRACT
In the present work, a new pathway of the insertion reactions of H2GeLiF with RH (R = F, OH, NH2) was investigated using DFT B3LYP and QCISD methods. The geometries of the stationary points on the potential energy surfaces in the reactions were optimized at the B3LYP/6-311 + G (d, p) level and then the single-point energies were calculated at the QCISD/6-311++G (d, p) level. The calculated results indicated that the initial step of all the reactions is the isomerization of the p-complex structure to a three-membered-ring structure. After isomerization, the insertion reactions of three-membered-ring H2GeLiF with RH (R = F, OH, NH2) take place. The QCISD/6-311++G (d, p)//B3LYP/6-311 + G (d, p) calculated potential energy barriers of the three reactions were 89.77, 137.40, and 167.45 kJ mol(-1), respectively. Under the same situation, the insertion reactions should occur easily in the following order H-F > H-OH > H-NH2. Compared with the direct insertion reactions of H2GeLiF with RH (R = F, OH, NH2), the two-step insertions have lower activation barriers and should be more favorable.
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MEDLINE
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En
Revista:
J Mol Model
Assunto da revista:
BIOLOGIA MOLECULAR
Ano de publicação:
2015
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Article