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Comparing the NBO charges of the reaction center P in the gas phase, the positive charge difference of P atom between P=S and P=O system is great, |Δδ| ≈ 0. 6: 1. 180 (1)< 1.793 (2) and 1.236 (3)< 1.844 (4), resulting in "thio effect". However, within each system, P=S or P=O system, the positive charge difference of P, |Δδ| = 0.05~0.06, is too small to be a decisive factor to decide the reactivity over steric factor
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