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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Frontier orbital consistent quantum capping potential (FOC-QCP) for bulky ligand of transition metal complexes
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Frontier orbital consistent quantum capping potential (FOC-QCP) for bulky ligand of transition metal complexes

机译：过渡金属配合物大配体的前沿轨道一致量子封盖电势（FOC-QCP）

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摘要

Chemically reasonable models of PR3 (R = Me, Et, Pr-i, and Bu-t) were constructed to apply the post Hartree-Fock method to large transition metal complexes. In this model, R is replaced by the H atom including the frontier orbital consistent quantum capping potential (FOC-QCP) which reproduces the frontier orbital energy of PR3. The steric effect is incorporated by the new procedure named steric repulsion correction (SRC). To examine the performance of this FOC-QCP method with the SRC,, the activation barriers and reaction energies of the reductive elimination reactions Of C2H6 and H-2 from M(R-I)(2)(PR32)(2) (M = Ni, Pd, or Pt; R-1 = Me for R-1 = Me, Et, or P-i(r), or R-1 = H for R-2 = Bu-t) were evaluated with the DFT[B3PW91], MP4(SDQ), and CCSD(T) methods. The FOC-QCP method reproduced well the DFT[B3PW91]- and MP4(SDQ)-calculated energy changes of the real complexes with PMe3. For more bulky phosphine, the SRC is important to present correct energy change, in which the MP2 method presents reliable steric repulsion correction like the CCSD(T) method because the systems calculated in the SRC do not include a transition metal element. The monomerization energy of [RhCl((PPr3)-Pr-i)(2)](2) and the coordination energies of CO, H-2, N-2, and C2H4 with [RhCl(P-i-Pr-3)(2)](2) were theoretically calculated by the CCSD(T) method combined with the FOC-QCP and the SRC. The CCSD(T)-calculated energies agree well with the experimental ones, indicating the excellent performance of the combination of the FOC-QCP with the SRC. On the other hand, the DFT[B3PW9 I]-calculated energies of the real complexes considerably deviate from the experimental ones.
机译：建立PR3的化学合理模型（R = Me，Et，Pr-i和Bu-t），以将后Hartree-Fock方法应用于大型过渡金属络合物。在此模型中，R被氢原子所取代，后者包含边界轨道一致的量子加盖电势（FOC-QCP），可再现PR3的边界轨道能量。空间效应被称为空间排斥校正（SRC）的新过程合并。若要检查此FOC-QCP方法与SRC的性能，M（RI）（2）（PR32）（2）中C2H6和H-2的还原消除反应的活化能垒和反应能（M = Ni ，Pd或Pt;对于R-1 = Me，Et或Pi（r），R-1 = Me;对于R-2 = Bu-t，R-1 = H）用DFT [B3PW91]进行了评估， MP4（SDQ）和CCSD（T）方法。 FOC-QCP方法很好地再现了DFT [B3PW91]-和MP4（SDQ）计算的与PMe3的实际配合物的能量变化。对于更庞大的磷化氢，SRC对于呈现正确的能量变化很重要，其中MP2方法像CCSD（T）方法一样提供可靠的空间排斥校正，因为在SRC中计算的系统不包含过渡金属元素。 [RhCl（（PPr3）-Pr-i）（2）]（2）的单体化能以及CO，H-2，N-2和C2H4与[RhCl（Pi-Pr-3）（ 2）]（2）理论上是通过CCSD（T）方法结合FOC-QCP和SRC进行计算的。 CCSD（T）计算得出的能量与实验结果吻合得很好，表明FOC-QCP与SRC组合的出色性能。另一方面，实际配合物的DFT [B3PW9 I]计算出的能量与实验值大不相同。

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