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Combined DFT Protocol for the Calculation of One-Bond 31P-31P Indirect Nuclear Spin-Spin Couplings
Svetlana A Kondrashova1, Shamil K Latypov1
1Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Kazan 420088, Tatarstan, Russia.
None:
The comparative analysis of calculated and experimental one-bond 31P-31P indirect nuclear spin-spin couplings for a wide range of structures, including P-P bonds, has shown that, on the whole, it is possible to estimate 1JPP fairly accurately using even modest levels of theory. However, in order to reduce systematic errors, it is necessary to carry out a linear correction procedure specific to different groups of compounds. Certain difficulties may arise only for diphosphanes (R1R2P-PR1R2) that are in solution in fast (in NMR time scale) exchange of conformers with close populations. In practice, a relatively simple PBE0/6-31G(d)//PBE0/6-31G(d) combination is sufficient for calculating the 1JPP with practically reliable accuracy. The efficiency of the proposed protocol is demonstrated using the example of more subtle structural features-the isomeric structure. The proposed approach allowed for the absolute sign of 1JPP in a number of cases where it is unknown experimentally.
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