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In this work, the geometry of triethylamine (the anchor for the computed pKa values) was optimized to a more stable configuration (ΔE = -2.7 kcal/mol). As a result, the computed pKa values for the P4N4 system are slightly larger than those reported previously.
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The geometry of a singlet diazene intermediate [2(NHNH)′]2+ was unstable during optimization (the proton on the proximal nitrogen transfers to the Cr center) and was not given further consideration in this report.
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A more detailed investigation of the dependence of 2[2(NNH2)′] + on the identity of the supporting ligand is beyond the scope of this report, but it is worth noting that when phosphine (PH3) is added as a ligand to the vacant axial position of the hydrazido intermediate in the P4N4 system (in order to mimic the P5 coordination environment in the P3N3 system), the structure of the Cr-N-N unit upon geometry optimization was similar to that found in the P3N3 system.
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