AIM/NBO Analysis of the Geminal Coupling Constants in the Stabilization of A‐Type Dimeric Proanthocyanidin: Angular Dependence

The angular dependence of the indirect short-range spin-spin coupling constants (SSCC), the geminal <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics><mml:mrow><mml:mi>J</mml:mi> <mml:mo>(</mml:mo> <mml:msub><mml:mrow><mml:mi>C</mml:mi></mml:mrow> <mml:mrow><mml:mn>3</mml:mn></mml:mrow> </mml:msub> <mml:mo>,</mml:mo> <mml:msub><mml:mrow><mml:mi>C</mml:mi></mml:mrow> <mml:mrow> <mml:msup><mml:mrow><mml:mn>1</mml:mn></mml:mrow> <mml:mrow><mml:mo>'</mml:mo></mml:mrow> </mml:msup> </mml:mrow> </mml:msub> <mml:mo>)</mml:mo></mml:mrow> <mml:annotation>$$ J\left({C}_3,{C}_{1&amp;#x0005E;{\prime }}\right) $$</mml:annotation></mml:semantics> </mml:math> , <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics><mml:mrow><mml:mi>J</mml:mi> <mml:mo>(</mml:mo> <mml:msub><mml:mrow><mml:mi>O</mml:mi></mml:mrow> <mml:mrow><mml:mn>1</mml:mn></mml:mrow> </mml:msub> <mml:mo>,</mml:mo> <mml:mi>O</mml:mi> <mml:mo>)</mml:mo></mml:mrow> <mml:annotation>$$ J\left({O}_1,O\right) $$</mml:annotation></mml:semantics> </mml:math> , and <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics><mml:mrow><mml:mi>J</mml:mi> <mml:mo>(</mml:mo> <mml:mi>O</mml:mi> <mml:mo>,</mml:mo> <mml:msub><mml:mrow><mml:mi>C</mml:mi></mml:mrow> <mml:mrow> <mml:msup><mml:mrow><mml:mn>1</mml:mn></mml:mrow> <mml:mrow><mml:mo>'</mml:mo></mml:mrow> </mml:msup> </mml:mrow> </mml:msub> <mml:mo>)</mml:mo></mml:mrow> <mml:annotation>$$ J\left(O,{C}_{1&amp;#x0005E;{\prime }}\right) $$</mml:annotation></mml:semantics> </mml:math> in A-type dimeric proanthocyanidin, was investigated using density functional theory. We studied the rotation of ring B around the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow> <mml:msub><mml:mrow><mml:mi>C</mml:mi></mml:mrow> <mml:mrow><mml:mn>2</mml:mn></mml:mrow> </mml:msub> <mml:mtext>-</mml:mtext> <mml:msub><mml:mrow><mml:mi>C</mml:mi></mml:mrow> <mml:mrow> <mml:msup><mml:mrow><mml:mn>1</mml:mn></mml:mrow> <mml:mrow><mml:mo>'</mml:mo></mml:mrow> </mml:msup> </mml:mrow> </mml:msub> </mml:mrow> <mml:annotation>$$ {C}_2\hbox{--} {C}_{1&amp;#x0005E;{\prime }} $$</mml:annotation></mml:semantics> </mml:math> bond. Therefore, we calculated hyperconjugative charge transfers and bond polarizations within the natural bond orbital (NBO) approach, performing a topological study based on Bader's theory, AIM (atoms in molecules), and analyzing the angular dependence of AIM/NBO parameters. The results describe a relationship between the geminal coupling that changes with angular variation and NBO charge transfers to the bonds involved in the coupling pathways that can explain the behavior of the former property. Based on AIM/NBO data, inductive and mesomeric effects were described and quantified, showing a clear correlation with the stabilization of the structure, demonstrating a resonance-assisted inductive effect. We also set out strong hyperconjugative interactions (anomeric effect) involving nonbonding electron pairs of oxygen atoms. This analysis of coupling constants supports previous models by other authors and shows the application in this particular case. Moreover, the SSCCs studied herein are used for identifying stable structures and conformational search analysis of flavonoids. Finally, our results show the relationship between SSCCs and the structure stabilization and charge delocalization effects.