New insights into the insertion reactions of germylenoid H2GeLiF with RH (R = F, OH, NH2).
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.
The Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering Yantai University, Yantai, 264005, People's Republic of China.
Bingfei
B
Yan
Wenzuo
W
Li
Cuiping
C
Xiao
Zhenbo
Z
Liu
Qingzhong
Q
Li
Jianbo
J
Cheng
D005857:Germanium / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D008094:Lithium / Q000737:chemistry; D008958:Models, Molecular; D011789:Quantum Theory; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D005857:Germanium; D014867:Water; D006859:Hydrogen; D008094:Lithium