Probing mechanism of metal catalyzed hydrolysis of Thymidylyl (3ʹ-O, 5ʹ-S) thymidine phosphodiester derivatives.
Mahboobeh Rahimian and Shridhar P. Gejji*
Department of Chemistry, University of Pune, Ganeshkhind, Pune 411007 (India)
Supplementary Information:
Table 1S B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘A’ and ‘B’ pathways for Li, Na and K catalyzed Tp-OCH2CF3(2) hydrolysis.
Table 2S B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘A’ and ‘B’pathways for Li, Na and K catalyzed Tp-OPh (o-Cl) (3) hydrolysis.
Table 3S B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘A’ and ‘B’ pathways for Li, Na and K catalyzed Tp-OPh(p-NO2) (4) hydrolysis.
Table 4S B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘B’ pathways for Li (W), Na (W) and K (W) catalyzed Tp-ST (1) hydrolysis.
Table 5S B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘A’ and ‘B’ pathways for Li (W), Na (W) and K (W) catalyzed Tp-OCH2CF3(2) hydrolysis.
Table 6S B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘A’ and ‘B’ pathways for Li (W), Na (W) and K (W) catalyzed Tp-OPh (o-Cl) (3) hydrolysis.
Table 7S B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘A’ and ‘B’ pathways for Li (W), Na (W) and K (W) catalyzed Tp-OPh(p-NO2) (4) hydrolysis.
Table 1S.B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘A’ and ‘B’pathways for Li, Na and K catalyzed Tp-OCH2CF3(2)hydrolysis
A / BLi / Li / Na / K
parameter / R / TS / P / R / TS / P / R / TS / P / R / TS / P
P1O3 / 1.717 / 1.806 / 3.970 / 1.703 / 1.755 / 4.102 / 1.694 / 1.767 / 4.225 / 1.672 / 1.772 / 4.934
P1O16 / 4.007 / 2.510 / 1.667 / 3.958 / 2.578 / 1.696 / 4.057 / 2.538 / 1.685 / 3.990 / 2.348 / 1.688
P1O4 / 1.555 / 1.568 / 1.535 / 1.523 / 1.526 / 1.503 / 1.516 / 1.522 / 1.507 / 1.518 / 1.521 / 1.505
P1O5 / 1.485 / 1.491 / 1.487 / 1.510 / 1.521 / 1.526 / 1.507 / 1.520 / 1.519 / 1.500 / 1.521 / 1.514
P1O2 / 1.593 / 1.606 / 1.644 / 1.592 / 1.612 / 1.599 / 1.613 / 1.629 / 1.618 / 1.644 / 1.673 / 1.633
O3M40 / 1.977 / 1.889 / 1.782 / 2.065 / 1.871 / 1.757 / 2.299 / 2.200 / 2.126 / 2.900 / 2.633 / 2.469
O16M41 / 1.649 / 1.698 / 2.076 / 1.669 / 1.708 / 1.944 / 2.040 / 2.075 / 2.298 / 2.406 / 2.348 / 2.683
O4M40 / 1.833 / 1.821 / 1.884 / 1.803 / 1.800 / 1.844 / 2.163 / 2.155 / 2.186 / 2.641 / 2.600 / 2.617
O5M41 / 1.850 / 1.830 / 1.806 / 2.200 / 2.173 / 2.148 / 2.831 / 2.506 / 2.538
O4M41 / 1.893 / 1.846 / 1.969
O3P1O16 / 147.4 / 171.6 / 71.2 / 151.6 / 177.2 / 144.0 / 163.1 / 175.4 / 159.0 / 167.9 / 174.1 / 127.8
O3P1O4 / 95.9 / 91.5 / 30.5 / 98.8 / 92.9 / 51.3 / 100.0 / 94.4 / 58.3 / 102.6 / 94.4 / 66.1
O3P1O5 / 109.2 / 101.8 / 146.9 / 107.7 / 102.3 / 118.4 / 109.0 / 101.2 / 100.2 / 113.1 / 99.6 / 124.6
O3P1O2 / 101.1 / 95.4 / 98.3 / 98.8 / 93.8 / 68.2 / 97.1 / 91.9 / 73.9 / 95.5 / 87.9 / 44.7
O3M40O4 / 79.2 / 81.5 / 97.6 / 78.4 / 80.9 / 139.0 / 66.9 / 67.5 / 116.4 / 53.2 / 55.2 / 126.2
O16M41O4 / 148.7 / 100.8 / 73.6
O5M41O16 / 134.3 / 101.0 / 80.4 / 116.3 / 82.6 / 67.4 / 98.1 / 66.0 / 57.1
P1O16M41 / 39.0 / 75.9 / 90.0 / 44.8 / 73.5 / 85.8 / 53.4 / 81.6 / 90.4 / 53.4 / 90.1 / 94.7
P1O3M 40 / 86.4 / 87.8 / 55.0 / 83.4 / 88.0 / 41.3 / 91.0 / 94.1 / 51.8 / 83.1 / 91.1 / 45.3
P1O16H24 / 161.9 / 101.3 / 113.8 / 158.6 / 107.3 / 114.5 / 154.2 / 100.1 / 113.1 / 158.7 / 96.7 / 110.7
M40O3C17 / 115.9 / 115.0 / 153.9 / 115.9 / 149.4 / 116.7 / 148.1 / 145.6 / 119.8 / 131.7 / 135.6 / 126.8
P1O3C17 / 120.1 / 120.5 / 150.9 / 121.6 / 121.5 / 157.7 / 120.7 / 120.2 / 160.2 / 119.8 / 118.8 / 165.6
Table 2S. B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘A’ and ‘B’pathways for Li, Na and K catalyzed Tp-OPh (o-Cl) (3) hydrolysis
A / BLi / Li / Na / K
parameter / R / TS / P / R / TS / P / R / TS / P / R / TS / P
P1O3 / 1.702 / 1.774 / 3.930 / 1.711 / 1.792 / 4.098 / 1.707 / 1.796 / 4.566 / 1.694 / 1.826 / 5.053
P1O16 / 4.206 / 2.611 / 1.694 / 4.012 / 2.618 / 1.688 / 4.058 / 2.586 / 1.689 / 4.477 / 2.519 / 1.687
P1O4 / 1.553 / 1.567 / 1.561 / 1.521 / 1.523 / 1.504 / 1.515 / 1.518 / 1.504 / 1.513 / 1.513 / 1.504
P1O5 / 1.480 / 1.484 / 1.483 / 1.504 / 1.511 / 1.523 / 1.506 / 1.512 / 1.516 / 1.502 / 1.513 / 1.513
P1O2 / 1.613 / 1.617 / 1.605 / 1.597 / 1.603 / 1.605 / 1.610 / 1.624 / 1.623 / 1.628 / 1.634 / 1.636
O3M40 / 1.907 / 1.830 / 1.764 / 1.963 / 1.894 / 1.774 / 2.301 / 2.228 / 2.131 / 2.721 / 2.662 / 2.481
O16M41 / 1.658 / 1.696 / 1.891 / 1.671 / 1.702 / 1.953 / 2.041 / 2.079 / 2.289 / 2.381 / 2.410 / 2.683
O4M40 / 1.868 / 1.859 / 1.862 / 1.824 / 1.8276 / 1.829 / 2.186 / 2.184 / 2.206 / 2.522 / 2.496 / 2.615
O5M41 / 1.842 / 1.834 / 1.798 / 2.199 / 2.167 / 2.177 / 2.573 / 2.544 / 2.543
O4M41 / 1.885 / 1.843 / 1.824
O3P1O16 / 138.1 / 166.7 / 141.5 / 149.3 / 178.3 / 148.9 / 163.5 / 174.9 / 131.1 / 93.1 / 172.8 / 126.5
O3P1O4 / 93.8 / 88.9 / 55.1 / 96.1 / 92.2 / 46.0 / 98.8 / 94.0 / 59.3 / 101.3 / 93.8 / 64.9
O3P1O5 / 114.2 / 106.2 / 104.1 / 109.4 / 101.5 / 112.4 / 110.1 / 101.1 / 125.8 / 111.0 / 102.5 / 126.2
O3P1O2 / 97.9 / 94.7 / 73.9 / 98.8 / 97.7 / 78.5 / 96.8 / 92.6 / 52.5 / 97.0 / 89.6 / 45.1
O3M40O4 / 78.1 / 78.9 / 130.8 / 78.8 / 80.2 / 128.1 / 66.1 / 66.9 / 135.4 / 56.3 / 56.5 / 130.0
O16M41O4 / 147.1 / 103.3 / 80.4
O5M41O16 / 134.0 / 103.3 / 79.8 / 115.4 / 84.5 / 67.3 / 102.5 / 69.0 / 57.1
P1O16M41 / 34.3 / 73.6 / 89.0 / 44.1 / 72.4 / 86.1 / 53.2 / 80.7 / 91.0 / 59.5 / 87.9 / 94.9
P1O3M 40 / 89.9 / 92.6 / 46.5 / 86.7 / 87.5 / 45.4 / 91.5 / 94.1 / 41.5 / 94.4 / 93.4 / 42.7
P1O16H24 / 164.2 / 104.1 / 114.5 / 159.8 / 111.5 / 116.0 / 154.3 / 101.2 / 112.6 / 143.2 / 100.4 / 110.9
M40O3C17 / 131.2 / 134.0 / 121.7 / 128.6 / 127.1 / 122.7 / 136.1 / 135.7 / 128.1 / 137.7 / 135.7 / 137.1
P1O3C17 / 129.4 / 131.3 / 168.1 / 129.7 / 129.1 / 166.9 / 128.8 / 130.0 / 169.6 / 127.9 / 126.9 / 145.8
Table 3S. B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘A’ and ‘B’ pathways for Li, Na and K catalyzedTp-OPh(p-NO2) (4)hydrolysis
A / BLi / Li / Na / K
parameter / R / TS / P / R / TS / P / R / TS / P / R / TS / P
P1O3 / 1.714 / 1.792 / 4.032 / 1.731 / 1.797 / 3.791 / 1.734 / 1.834 / 4.090 / 1.712 / 1.826 / 5.116
P1O16 / 4.169 / 2.692 / 1.688 / 4.039 / 2.696 / 1.682 / 4.715 / 2.690 / 1.691 / 4.423 / 2.613 / 1.683
P1O4 / 1.556 / 1.565 / 1.565 / 1.520 / 1.522 / 1.520 / 1.510 / 1.510 / 1.507 / 1.510 / 1.511 / 1.506
P1O5 / 1.481 / 1.482 / 1.482 / 1.504 / 1.507 / 1.511 / 1.503 / 1.510 / 1.517 / 1.498 / 1.504 / 1.512
P1O2 / 1.603 / 1.606 / 1.605 / 1.589 / 1.597 / 1.603 / 1.605 / 1.608 / 1.614 / 1.634 / 1.637 / 1.636
O3M40 / 1.908 / 1.841 / 1.681 / 1.952 / 1.888 / 1.754 / 2.318 / 2.245 / 2.080 / 2.799 / 2.771 / 2.430
O16M41 / 1.654 / 1.688 / 1.889 / 1.666 / 1.695 / 2.104 / 2.031 / 2.056 / 2.330 / 2.417 / 2.413 / 2.700
O4M40 / 1.813 / 1.803 / 1.857 / 1.785 / 1.789 / 1.820 / 2.142 / 2.132 / 2.203 / 2.572 / 2.520 / 2.593
O5M41 / 1.850 / 1.846 / 1.853 / 2.205 / 2.199 / 2.149 / 2.702 / 2.555 / 2.546
O4M41 / 1.897 / 1.857 / 1.833
O3P1O16 / 140.1 / 166.3 / 145.1 / 145.7 / 179.2 / 76.9 / 136.4 / 176.5 / 174.3 / 88.0 / 170.8 / 130.0
O3P1O4 / 94.3 / 90.1 / 53.6 / 95.4 / 92.5 / 57.4 / 98.7 / 93.7 / 68.3 / 100.3 / 94.2 / 62.3
O3P1O5 / 113.5 / 106.8 / 97.3 / 109.3 / 102.6 / 81.1 / 108.2 / 102.4 / 85.3 / 108.7 / 101.6 / 124.0
O3P1O2 / 98.5 / 95.3 / 80.9 / 100.3 / 98.7 / 168.0 / 102.5 / 95.4 / 73.9 / 103.1 / 94.0 / 48.3
O3M40O4 / 80.2 / 81.6 / 142.4 / 80.1 / 81.6 / 129.9 / 67.0 / 68.0 / 125.0 / 54.7 / 55.0 / 133.3
O16M41O4 / 149.5 / 105.3 / 80.3
O5M41O16 / 132.8 / 104.8 / 75.7 / 130.0 / 84.5 / 66.7 / 117.3 / 72.8 / 56.8
P1O16M41 / 34.9 / 72.2 / 89.3 / 43.9 / 71.1 / 84.0 / 40.9 / 79.7 / 90.0 / 50.6 / 86.1 / 94.7
P1O3M 40 / 88.4 / 89.5 / 39.1 / 85.8 / 86.5 / 47.2 / 90.2 / 91.4 / 49.9 / 94.8 / 94.7 / 41.0
P1O16H24 / 162.9 / 107.4 / 115.0 / 159.2 / 119.8 / 114.4 / 171.6 / 105.4 / 112.4 / 158.7 / 100.6 / 111.1
M40O3C17 / 146.7 / 143.8 / 169.8 / 148.0 / 144.6 / 134.9 / 143.8 / 139.1 / 153.0 / 139.3 / 138.2 / 175.8
P1O3C17 / 124.7 / 126.2 / 145.1 / 126.0 / 128.2 / 87.7 / 125.5 / 129.3 / 108.5 / 125.5 / 126.8 / 143.2
Table 4S. B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘B’ pathways forLi (W), Na (W) and K (W) catalyzed Tp-ST(1) hydrolysis
Li / Na / Kparameter / R / TS / P / R / TS / P / R / TS / P
P1 S3 / 2.150 / 2.630 / 5.249 / 2.169 / 2.473 / 6.238 / 2.175 / 2.407 / 6.202
P1O16 / 3.851 / 1.854 / 1.704 / 4.145 / 2.283 / 1.695 / 4.368 / 2.159 / 1.655
P1O4 / 1.529 / 1.535 / 1.498 / 1.523 / 1.524 / 1.500 / 1.522 / 1.530 / 1.500
P1O5 / 1.513 / 1.535 / 1.515 / 1.513 / 1.528 / 1.514 / 1.512 / 1.522 / 3.805
P1O2 / 1.630 / 1.648 / 1.619 / 1.634 / 1.642 / 1.624 / 1.638 / 1.660 / 1.641
S3M40 / 3.074 / 2.415 / 2.430 / 2.982 / 2.827 / 2.737 / 3.359 / 3.161 / 3.240
O16M41 / 1.825 / 1.928 / 2.005 / 2.194 / 2.098 / 2.331 / 2.555 / 2.646 / 2.675
O4M40 / 1.852 / 1.923 / 1.901 / 2.262 / 2.265 / 2.242 / 2.631 / 2.640 / 2.734
O5M41 / 1.853 / 1.797 / 1.846 / 2.206 / 2.276 / 2.245 / 2.619 / 2.516 / 2.651
O6M40 / 1.953 / 2.009 / 2.039 / 2.303 / 2.305 / 2.349 / 2.721 / 2.729 / 2.751
O7M41 / 1.989 / 1.996 / 1.891 / 2.270 / 2.311 / 2.236 / 2.611 / 2.620 / 2.627
S3P1O16 / 161.4 / 173.4 / 118.3 / 159.7 / 172.0 / 125.9 / 161.1 / 171.6 / 95.0
S3P1O4 / 106.0 / 89.0 / 25.9 / 106.5 / 99.8 / 20.3 / 107.2 / 96.1 / 69.3
S3P1O5 / 112.6 / 90.7 / 99.2 / 111.0 / 100.1 / 108.6 / 110.6 / 95.7 / 151.5
S3P1O2 / 93.7 / 80.3 / 124.9 / 93.6 / 87.6 / 109.3 / 93.6 / 84.0 / 42.1
S3M40O4 / 68.9 / 87.5 / 131.6 / 67.7 / 69.9 / 154.6 / 58.6 / 61.2 / 156.0
O5M41O16 / 128.3 / 82.2 / 78.7 / 118.5 / 78.2 / 65.6 / 105.2 / 60.8 / 55.5
P1O16M41 / 48.8 / 85.4 / 85.3 / 52.2 / 86.9 / 92.3 / 58.2 / 92.2 / 96.9
P1S3M 40 / 64.6 / 70.0 / 29.8 / 73.4 / 76.4 / 16.6 / 77.1 / 81.3 / 22.7
P1O16H24 / 121.2 / 104.8 / 112.1 / 126.2 / 98.7 / 111.0 / 129.6 / 98.1 / 112.3
M40S3C17 / 95.1 / 96.9 / 91.4 / 100.4 / 99.2 / 90.3 / 104.7 / 100.8 / 88.7
P1S3C17 / 103.7 / 111.5 / 118.9 / 105.6 / 107.8 / 106.7 / 105.6 / 109.6 / 92.0
Table 5S. B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along‘B’ pathways forLi (W), Na (W) and K (W) catalyzed Tp-OCH2CF3(2) hydrolysis
Li / Na / Kparameter / R / TS / P / R / TS / P / R / TS / P
P1 O3 / 1.688 / 1.780 / 4.010 / 1.682 / 1.803 / 4.802 / 1.669 / 1.812 / 4.789
P1O16 / 3.990 / 2.274 / 1.692 / 3.975 / 2.399 / 1.682 / 4.154 / 2.066 / 1.654
P1O4 / 1.518 / 1.531 / 1.503 / 1.512 / 1.520 / 1.504 / 1.516 / 1.541 / 1.506
P1O5 / 1.506 / 1.530 / 1.524 / 1.506 / 1.517 / 1.512 / 1.501 / 1.522 / 1.517
P1O2 / 1.608 / 1.629 / 1.608 / 1.634 / 1.638 / 1.642 / 1.646 / 1.677 / 1.654
O3M40 / 2.066 / 1.900 / 1.739 / 2.444 / 2.166 / 2.171 / 2.878 / 2.615 / 2.728
O16M41 / 1.805 / 1.863 / 1.996 / 2.199 / 2.419 / 2.345 / 2.597 / 2.827 / 2.650
O4M40 / 1.824 / 1.824 / 1.876 / 2.221 / 2.249 / 2.243 / 2.647 / 2.630 / 2.618
O5M41 / 1.851 / 1.819 / 1.830 / 2.210 / 2.139 / 2.246 / 2.813 / 2.614 / 2.565
O6M40 / 1.891 / 1.903 / 1.972 / 2.288 / 2.333 / 2.297 / 2.674 / 2.705 / 2.682
O7M41 / 1.982 / 1.949 / 1.899 / 2.270 / 2.260 / 2.280 / 2.621 / 2.629 / 2.768
O3P1O16 / 156.1 / 175.4 / 153.5 / 169.3 / 176.0 / 123.8 / 167.1 / 172.4 / 70.1
O3P1O4 / 98.1 / 91.4 / 51.8 / 101.0 / 83.9 / 60.9 / 103.1 / 91.2 / 77.0
O3P1O5 / 108.8 / 99.2 / 106.7 / 109.5 / 85.4 / 130.9 / 112.9 / 97.9 / 160.1
O3P1O2 / 98.9 / 90.9 / 76.1 / 97.1 / 81.4 / 46.8 / 95.8 / 86.1 / 53.3
O3M40O4 / 76.8 / 79.3 / 131.7 / 63.7 / 75.4 / 151.4 / 53.5 / 54.6 / 122.4
O5M41O16 / 127.3 / 90.6 / 79.1 / 114.2 / 66.2 / 65.3 / 100.5 / 55.7 / 57.2
P1O16M41 / 47.4 / 79.1 / 85.5 / 54.9 / 88.6 / 92.1 / 51.2 / 75.9 / 93.4
P1O3M 40 / 85.4 / 89.0 / 46.1 / 89.4 / 87.5 / 30.2 / 87.0 / 81.2 / 44.7
P1O16H24 / 122.9 / 97.4 / 113.0 / 123.9 / 105.5 / 112.3 / 139.8 / 102.2 / 110.8
M40O3C17 / 151.3 / 148.6 / 154.0 / 149.8 / 123.6 / 151.5 / 138.1 / 136.6 / 123.1
P1O3C17 / 120.9 / 120.2 / 158.0 / 120.4 / 118.7 / 150.8 / 119.5 / 118.4 / 131.9
Table 6S. B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along‘B’ pathways forLi (W), Na (W) and K (W) catalyzed Tp-OPh (o-Cl) (3) hydrolysis
Li / Na / Kparameter / R / TS / P / R / TS / P / R / TS / P
P1 O3 / 1.709 / 1.807 / 4.188 / 1.694 / 1.849 / 3.472 / 1.688 / 1.853 / 5.151
P1O16 / 3.930 / 2.313 / 1.686 / 4.011 / 2.243 / 1.646 / 4.143 / 2.236 / 1.678
P1O4 / 1.518 / 1.528 / 1.507 / 1.510 / 1.523 / 1.524 / 1.519 / 1.529 / 1.503
P1O5 / 1.500 / 1.518 / 1.516 / 1.504 / 1.515 / 1.515 / 1.501 / 1.512 / 1.519
P1O2 / 1.604 / 1.624 / 1.611 / 1.629 / 1.646 / 1.627 / 1.629 / 1.646 / 1.503
O3M40 / 1.988 / 1.900 / 1.824 / 2.425 / 2.262 / 2.202 / 2.887 / 2.686 / 2.551
O16M41 / 1.810 / 1.866 / 1.975 / 2.197 / 2.253 / 2.358 / 2.621 / 2.689 / 2.729
O4M40 / 1.920 / 1.906 / 1.823 / 2.248 / 2.234 / 2.269 / 2.608 / 2.591 / 2.630
O5M41 / 1.868 / 1.817 / 1.516 / 2.209 / 2.154 / 2.201 / 2.820 / 2.743 / 2.690
O6M40 / 1.904 / 1.932 / 1.976 / 2.300 / 2.308 / 2.296 / 2.712 / 2.715 / 2.631
O7M41 / 1.991 / 1.953 / 1.901 / 2.270 / 2.247 / 2.254 / 2.573 / 2.618 / 2.622
O3P1O16 / 159.8 / 176.2 / 83.8 / 169.7 / 174.6 / 84.8 / 169.7 / 173.9 / 134.6
O3P1O4 / 96.4 / 90.9 / 44.0 / 99.6 / 91.6 / 68.4 / 101.7 / 93.1 / 64.7
O3P1O5 / 108.1 / 98.9 / 165.9 / 110.9 / 97.3 / 112.9 / 112.9 / 98.7 / 118.7
O3P1O2 / 102.4 / 92.9 / 84.8 / 96.8 / 90.3 / 93.7 / 96.4 / 87.9 / 48.3
O3M40O4 / 76.1 / 77.6 / 127.8 / 63.1 / 65.4 / 92.8 / 53.6 / 55.7 / 130.7
O5M41O16 / 132.5
/ 91.6 / 79.6 / 114.5 / 74.3 / 67.0 / 98.3 / 57.6 / 54.9
P1O16M41 / 46.0 / 78.4 / 85.5 / 54.3 / 85.8 / 88.9 / 51.6 / 76.8 / 98.1
P1O3M 40 / 89.0 / 90.9 / 44.4 / 90.8 / 95.5 / 69.3 / 91.9 / 98.0 / 41.0
P1O16H24 / 125.1 / 101.1 / 114.7 / 125.0 / 98.9 / 113.3 / 138.6 / 103.6 / 110.5
M40O3C17 / 132.7 / 132.7 / 143.0 / 137.7 / 134.8 / 133.7 / 138.5 / 135.8 / 157.3
P1O3C17 / 129.4 / 129.6 / 111.5 / 129.7 / 127.9 / 140.2 / 127.1 / 126.2 / 130.7
Table 7S. B3LYP/6-31++G (d, p) geometrical parameters (bond lengths in Å and bond angles in °) of reactant, transition state, and product along ‘B’ pathways forLi (W), Na (W) and K (W) catalyzed Tp-OPh(p-NO2) (4) hydrolysis
Li / Na / Kparameter / R / TS / P / R / TS / P / R / TS / P
P1 O3 / 1.713 / 1.817 / 3.320 / 1.714 / 1.856 / 4.453 / 1.717 / 1.874 / 4.311
P1O16 / 3.384 / 2.369 / 1.648 / 4.024 / 2.347 / 1.678 / 4.292 / 2.343 / 1.696
P1O4 / 1.516 / 1.525 / 1.516 / 1.510 / 1.519 / 1.508 / 1.508 / 1.516 / 1.512
P1O5 / 1.503 / 1.513 / 1.519 / 1.502 / 1.510 / 1.513 / 1.501 / 1.507 / 1.511
P1O2 / 1.615 / 1.624 / 1.631 / 1.629 / 1.633 / 1.622 / 1.717 / 1.637 / 1.626
O3M40 / 2.119 / 1.939 / 1.863 / 2.431 / 2.286 / 2.245 / 2.869 / 2.690 / 2.483
O16M41 / 1.824 / 1.855 / 1.950 / 2.185 / 2.232 / 2.476 / 2.559 / 2.607 / 3.568
O4M40 / 1.828 / 1.841 / 1.840 / 2.189 / 2.183 / 2.168 / 2.549 / 2.540 / 2.621
O5M41 / 1.885 / 1.838 / 1.891 / 2.313 / 2.178 / 2.225 / 2.729 / 2.554 / 2.578
O6M40 / 1.877
/ 1.895 / 1.932 / 2.235 / 2.248 / 2.282 / 2.654 / 2.669 / 2.733
O7M41 / 1.972
/ 1.950 / 1.892 / 2.292 / 2.260 / 2.250 / 2.626 / 2.611 / 2.669
O3P1O16 / 173.5 / 174.3 / 46.3 / 153.6 / 172.9 / 93.8 / 151.3 / 171.8 / 171.0
O3P1O4 / 96.9 / 90.9 / 105.6 / 99.4 / 92.0 / 56.2 / 100.5 / 92.3 / 69.7
O3P1O5 / 109.7 / 101.0 / 128.8 / 110.0 / 99.2 / 74.0 / 109.4 / 99.1 / 82.5
O3P1O2 / 100.4 / 94.6 / 119.4 / 102.0 / 92.7 / 158.9 / 101.3 / 91.6 / 73.6
O3M40O4 / 75.3 / 78.4 / 105.6 / 64.1 / 66.1 / 120.2 / 54.1 / 56.0 / 104.7
O5M41O16 / 120.6 / 93.5 / 80.1 / 124.8 / 76.9 / 63.3 / 114.0 / 64.7 / 45.9
P1O16M41 / 56.1 / 76.9 / 85.8 / 46.4 / 84.0 / 89.0 / 52.2 / 89.5 / 78.9
P1O3M 40 / 85.1 / 88.6 / 64.1 / 90.4 / 93.4 / 45.8 / 92.8 / 96.5 / 57.9
P1O16H24 / 118.6 / 101.4 / 111.4 / 138.6 / 101.0 / 111.8 / 140.1 / 89.5 / 109.6
M40O3C17 / 146.2 / 142.4 / 140.6 / 143.3 / 138.9 / 136.5 / 140.6 / 135.6 / 163.3
P1O3C17 / 128.2 / 128.9 / 154.4 / 126.2 / 127.7 / 90.9 / 125.7 / 127.4 / 105.8