. Author manuscript; available in PMC: 2021 Dec 4.

Published in final edited form as: ACS Catal. 2020 Nov 16;10(23):13932–13945. doi: 10.1021/acscatal.0c03764

Table 4:

Changes in the natural charge of O_lg in the phosphoryl transfer transition state and product state relative to the reactant state for phosphate and phosphonate hydrolysis in water and PP1.

	pK_a	Phosphate-Nuc_H₂O			Phosphonate-Nuc_H₂O

Substrate	LG pK_a	Δq(O_lg)_TS	Δq(O_lg)_PS	Ratio	Δq(O_lg)_TS	Δq(O_lg)_PS	Ratio

pNPP/pNPMP	7.0	0.07	0.10	0.74	0.04	0.07	0.58
pCNPP/pCNPMP	8.0	0.06	0.07	0.82	0.03	0.05	0.64
mCNPP/mCNPMP	8.6	0.05	0.05	0.91	0.02	0.03	0.68
mCLPP/mCLPMP	8.8	0.05	0.05	0.89	0.02	0.03	0.72
pCLPP/pCLPMP	9.3	0.04	0.03	1.54	0.02	0.03	0.74
PP/PMP	10.0	0.04	0.03	1.59	0.02	0.02	0.82
pMPP/pMPMP	10.2	0.04	0.02	1.69	0.02	0.02	0.84

	pK_a	Phosphate-Nuc_OH⁻			Phosphonate-Nuc_OH⁻

Substrate	LG pK_a	Δq(O_lg)_TS	Δq(O_lg)_PS	Ratio	Δq(O_lg)_TS	Δq(O_lg)_PS	Ratio

pNPP/pNPMP	7.0	0.08	0.07	1.12	0.01	0.11	0.06
pCNPP/pCNPMP	8.0	0.07	0.05	1.46	0.01	0.07	0.05
mCNPP/mCNPMP	8.6	0.05	0.02	3.00	0.00	0.05	0.02
mCLPP/mCLPMP	8.8	0.05	0.02	2.90	0.00	0.04	0.03
pCLPP/pCLPMP	9.3	0.05	0.02	3.02	0.00	0.04	0.00
PP/PMP	10.0	0.05	0.01	3.75	0.00	0.03	0.00
pMPP/pMPMP	10.2	0.05	0.01	6.80	0.00	0.02	0.00

	pK_a	PP1-Phosphate			PP1-Phosphonate

Substrate	LG pK_a	Δq(O_lg)_TS	Δq(O_lg)_PS	Ratio	Δq(O_lg)_TS	Δq(O_lg)_PS	Ratio

pNPP/pNPMP	7.0	0.03	0.08	0.38	0.01	0.05	0.23
pCNPP/pCNPMP	8.0	0.02	0.05	0.48	0.02	0.04	0.37
mCNPP/mCNPMP	8.6	0.03	0.04	0.75	0.01	0.04	0.29
mCLPP/mCLPMP	8.8	0.03	0.03	0.78	0.01	0.03	0.45
pCLPP/pCLPMP	9.3	0.02	0.03	0.75	0.01	0.01	0.86
PP/PMP	10.0	0.02	0.05	0.46	0.01	0.01	0.89
pMPP/pMPMP	10.2	0.02	0.04	0.58	0.01	0.01	1.39