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Complexes H2 CO:PXH2 and HCO2 H : PXH2 for X=NC, F, Cl, CN, OH, CCH, CH3 , and H: Pnicogen Bonds and Hydrogen Bonds.
ChemPhysChem ( IF 2.3 ) Pub Date : 2020-03-17 , DOI: 10.1002/cphc.202000099 Janet E Del Bene 1 , Ibon Alkorta 2 , José Elguero 2
ChemPhysChem ( IF 2.3 ) Pub Date : 2020-03-17 , DOI: 10.1002/cphc.202000099 Janet E Del Bene 1 , Ibon Alkorta 2 , José Elguero 2
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Ab initio MP2/aug’‐cc‐pVTZ calculations have been carried out to investigate H2CO : PXH2 pnicogen‐bonded complexes and HCO2H : PXH2 complexes that are stabilized by pnicogen bonds and hydrogen bonds, with X=NC, F, Cl, CN, OH, CCH, CH3, and H. The binding energies of these complexes exhibit a second‐order dependence on the O−P distance. DFT‐SAPT binding energies correlate linearly with MP2 binding energies. The HCO2H : PXH2 complexes are stabilized by both a pnicogen bond and a hydrogen bond, resulting in greater binding energies for the HCO2H : PXH2 complexes compared to H2CO : PXH2. Neither the O−P distance across the pnicogen bond nor the O−P distance across the hydrogen bond correlates with the binding energies of these complexes. The nonlinearity of the hydrogen bonds suggests that they are relatively weak bonds, except for complexes in which the substituent X is either CH3 or H. The pnicogen bond is the more important stabilizing interaction in the HCO2H : PXH2 complexes except when the substituent X is a more electropositive group. EOM‐CCSD spin‐spin coupling constants 1pJ(O−P) across pnicogen bonds in H2CO:PXH2 and HCO2H : PXH2 complexes increase as the O−P distance decreases, and exhibit a second order dependence on that distance. There is no correlation between 2hJ(O−P) and the O−P distance across the hydrogen bond in the HCO2H : PXH2 complexes. 2hJ(O−P) coupling constants for complexes with X=CH3 and H have much greater absolute values than anticipated from their O−P distances.
中文翻译：
配合物H2 CO：PXH2和HCO2 H：X = NC，F，Cl，CN，OH，CCH，CH3和H时的PXH2：Pnicogen键和氢键。
已经进行了从头算MP2 / aug'-cc-pVTZ的计算，以研究通过Pnicogen键和氢键稳定的H 2 CO：PXH 2药原键合配合物和HCO 2 H：PXH 2配合物，X = NC， F，Cl，CN，OH，CCH，CH 3和H。这些配合物的结合能表现出对O-P距离的二级依赖性。DFT-SAPT结合能与MP2结合能线性相关。HCO 2 H：PXH 2配合物通过pnicogen键和氢键稳定，因此与H 2相比，HCO 2 H：PXH 2配合物的结合能更高CO：PXH 2。穿过成药原键的O-P距离和穿过氢键的O-P距离均与这些复合物的结合能无关。氢键的非线性表明它们是相对较弱的键，但取代基X的取代基为CH 3或H的络合物除外。胶料原键是HCO 2 H：PXH 2络合物中更重要的稳定相互作用，除了取代基X是更正电的基团。在H 2 CO：PXH 2和HCO 2 H：PXH 2中，跨气生原键的EOM‐CCSD自旋旋转耦合常数1p J（OP）随着O-P距离的减小，复合物增加，并且表现出对该距离的二阶依赖性。在2h J（OP ）和HCO 2 H：PXH 2络合物中氢键之间的O-P距离之间没有相关性。X = CH 3和H的配合物的2h J（OP）耦合常数的绝对值比其O-P距离所期望的要大得多。
更新日期：2020-03-17
中文翻译：
配合物H2 CO：PXH2和HCO2 H：X = NC，F，Cl，CN，OH，CCH，CH3和H时的PXH2：Pnicogen键和氢键。
已经进行了从头算MP2 / aug'-cc-pVTZ的计算，以研究通过Pnicogen键和氢键稳定的H 2 CO：PXH 2药原键合配合物和HCO 2 H：PXH 2配合物，X = NC， F，Cl，CN，OH，CCH，CH 3和H。这些配合物的结合能表现出对O-P距离的二级依赖性。DFT-SAPT结合能与MP2结合能线性相关。HCO 2 H：PXH 2配合物通过pnicogen键和氢键稳定，因此与H 2相比，HCO 2 H：PXH 2配合物的结合能更高CO：PXH 2。穿过成药原键的O-P距离和穿过氢键的O-P距离均与这些复合物的结合能无关。氢键的非线性表明它们是相对较弱的键，但取代基X的取代基为CH 3或H的络合物除外。胶料原键是HCO 2 H：PXH 2络合物中更重要的稳定相互作用，除了取代基X是更正电的基团。在H 2 CO：PXH 2和HCO 2 H：PXH 2中，跨气生原键的EOM‐CCSD自旋旋转耦合常数1p J（OP）随着O-P距离的减小，复合物增加，并且表现出对该距离的二阶依赖性。在2h J（OP ）和HCO 2 H：PXH 2络合物中氢键之间的O-P距离之间没有相关性。X = CH 3和H的配合物的2h J（OP）耦合常数的绝对值比其O-P距离所期望的要大得多。
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