SUPPLEMENTARY INFORMATION
Study of behaviour of Ni(III) macrocyclic complexes in acidic aqueous medium through kinetic measurement involving hydrogen peroxide oxidation and DFT calculations
ANURADHA SANKARAN,a,b E J PADMA MALARc,* and VENKATAPURAM RAMANUJAM VIJAYARAGHAVANa,*
a Department of Physical Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
b Department of Chemistry, PSNA college of Engineering and Technology, Kothandaraman Nagar, Dindigul, Tamilnadu 624 622, India
c National Centre for Ultrafast Processes, University of Madras, Taramani Campus, Chennai 600 113, India
Email: ; ;
*For correspondence
Table of Contents:
Figure S1. Complete BP86/def2-TZVP optimzed geometries of Ni(III) acetate complexes 1 [NiIIIL1(SO4)(OAc)] and 2 [NiIIIL2(SO4)(OAc)] in aqueous medium. Hydrogen bonds are denoted by dotted lines. / 2Table S1. Cartesian Coordinates (Angström) of BP86/def2-TZVP optimized geometries / 3
Table S2. BP86/TZVP gas-phase optimized Cartesian coordinates / 8
1
2
Figure S1. Complete BP86/def2-TZVP optimzed geometries of Ni(III) acetate complexes 1 [NiIIIL1(SO4)(OAc)] and 2 [NiIIIL2(SO4)(OAc)] in aqueous medium. Hydrogen bonds are denoted by dotted lines.
Table S1. Cartesian Coordinates (Angström) of BP86/def2-TZVP optimized geometries
[NiIIIL1(SO4)(OAc)] aqueous medium
Total Energy= -3051.537816 hartree; Dispersion energy= -79.60 kcal/mol
Ni -0.287024 0.015361 0.022032
N -0.071643 -1.232405 -1.509729
N 0.313303 1.439254 -1.220950
N -0.503590 1.249734 1.564910
N -0.864660 -1.420952 1.262431
C -1.314049 0.544947 2.587338
C -0.821166 -0.878840 2.639455
C 0.167266 0.908783 -2.595964
C 0.666011 -0.513042 -2.583593
C -0.284956 2.780479 -1.093557
C -0.972397 2.628351 1.333222
C -0.124536 3.356197 0.304128
C 0.505860 -2.570365 -1.252935
C -0.183526 -2.725168 1.174874
C -0.283592 -3.342210 -0.210699
H -0.896743 0.954570 -2.867423
H 1.733029 -0.558224 -2.324595
H -1.348060 2.703354 -1.362005
H 1.545111 -2.410320 -0.932555
H -1.221377 1.045914 3.562203
H -1.436793 -1.496155 3.310600
H -2.365307 0.589927 2.271697
H 0.220423 -0.915712 2.987500
H 0.736607 1.529314 -3.304703
H 0.509072 -1.013160 -3.550188
H 0.515331 -3.121646 -2.207446
H 0.207133 3.437957 -1.829444
H 0.484006 1.254223 1.863467
H 1.344079 1.491327 -0.978245
H -1.051922 -1.337675 -1.802018
H -1.870830 -1.508576 0.944919
H -0.644286 -3.395942 1.919022
H 0.868106 -2.570868 1.454879
H -0.948047 3.163468 2.296381
H -2.018223 2.568276 1.000953
O 2.930133 1.391033 -0.451305
S 3.039922 0.065824 0.263739
O 3.389750 -1.010555 -0.703180
O 4.017929 0.151502 1.376215
O 1.668803 -0.244203 0.886146
O -3.382535 -1.311692 0.194899
C -3.315781 -0.252992 -0.487879
O -2.247134 0.437172 -0.681702
C -4.566018 0.300841 -1.150287
H -4.803502 1.280954 -0.712150
H -4.381217 0.458551 -2.221523
H -5.416400 -0.376182 -1.012686
H -0.439253 4.408605 0.283289
H 0.935954 3.346100 0.604142
H 0.121599 -4.362465 -0.162169
H -1.338795 -3.435953 -0.516085
------
[NiIIIL2(SO4)(OAc)] aqueous medium
Total Energy= -3391.451220 hartree; Dispersion energy=-98.39 kcal/mol
Ni 0.058813 0.576518 0.007246
N -1.151955 0.071059 -1.474781
N 1.528604 0.308904 -1.273702
N 1.234632 1.106301 1.504554
N -1.428663 0.807657 1.280135
C 0.394291 1.759751 2.536042
C -0.863248 0.927964 2.644402
C 0.944244 0.353108 -2.636458
C -0.325680 -0.464557 -2.590900
C 2.695397 1.223150 -1.124843
C 2.477004 1.868696 1.170533
N 3.291210 1.202663 0.188180
C -2.289587 -0.816407 -1.125629
C -2.503499 -0.202027 1.198736
N -3.095818 -0.171023 -0.118192
H 0.732999 1.401560 -2.886963
H -0.108903 -1.516963 -2.362685
H 2.340740 2.239324 -1.337308
H -1.847022 -1.779445 -0.815461
H 0.932156 1.816237 3.493528
H -1.598940 1.386505 3.321358
H 0.168034 2.780184 2.199095
H -0.628205 -0.080645 3.012528
H 1.657058 -0.049703 -3.371414
H -0.883902 -0.411296 -3.536237
H -2.901312 -0.969505 -2.027957
H 3.438086 0.945428 -1.886868
H 1.484256 0.162953 1.837137
H 1.813665 -0.688542 -1.083474
H -1.533613 0.988374 -1.740061
H -1.788291 1.750929 0.955934
H -3.276029 0.050584 1.941679
H -2.053350 -1.175655 1.463140
H 3.053085 1.997416 2.100025
H 2.159943 2.849959 0.796126
O 1.977353 -2.376881 -0.767276
C 3.779571 -0.103347 0.676868
H 4.297942 0.082412 1.628616
H 2.943085 -0.791825 0.894030
C 4.703849 -0.858193 -0.288108
H 5.747955 -0.538143 -0.171101
H 4.418127 -0.667715 -1.336527
O 4.650619 -2.261593 -0.013760
H 3.707269 -2.514275 -0.198485
C -4.529004 -0.449857 -0.177985
H -5.040767 0.236734 0.513362
H -4.881290 -0.216196 -1.194185
C -4.908013 -1.890812 0.168591
H -4.575301 -2.135043 1.193390
H -4.412327 -2.591611 -0.527131
O -6.335804 -1.992764 0.060324
H -6.586238 -2.905908 0.286417
S 0.850330 -2.708589 0.200160
O -0.281023 -3.307138 -0.551972
O 1.346504 -3.590112 1.280143
O 0.394987 -1.393535 0.849199
O -1.895936 3.312036 0.295817
C -0.901663 3.467942 -0.460886
O -0.011961 2.569286 -0.712662
C -0.675558 4.798985 -1.156813
H 0.272063 5.234468 -0.808878
H -0.583979 4.640711 -2.240019
H -1.496600 5.493927 -0.948964
------
[NiIIIL1(SO4)(OAc)] gas-phase
Total Energy= -3051.476323 hartree; Dispersion energy= -80.56 kcal/mol
Ni -0.285229 0.020337 0.013615
N -0.070450 -1.240361 -1.529276
N 0.333341 1.421486 -1.212226
N -0.503535 1.271318 1.576138
N -0.879725 -1.406805 1.246908
C -1.336410 0.569504 2.570894
C -0.855316 -0.863272 2.620593
C 0.178175 0.912124 -2.588149
C 0.669025 -0.514819 -2.596554
C -0.247177 2.764355 -1.072493
C -0.894163 2.670721 1.369056
C -0.026121 3.345765 0.317393
C 0.520770 -2.569138 -1.261110
C -0.160253 -2.690805 1.173474
C -0.258780 -3.332431 -0.203082
H -0.886411 0.975068 -2.864927
H 1.735242 -0.566086 -2.323549
H -1.321550 2.708876 -1.309787
H 1.561057 -2.384472 -0.948533
H -1.265710 1.052644 3.560171
H -1.484766 -1.476151 3.285916
H -2.382304 0.621579 2.234635
H 0.183534 -0.904015 2.979185
H 0.760019 1.534956 -3.287643
H 0.514988 -1.001883 -3.572908
H 0.539010 -3.138653 -2.207014
H 0.235262 3.415595 -1.822592
H 0.500827 1.182353 1.826109
H 1.409355 1.460535 -0.933251
H -1.057074 -1.339780 -1.801956
H -1.884460 -1.508181 0.905082
H -0.590762 -3.367496 1.932678
H 0.890306 -2.493691 1.433606
H -0.822153 3.210107 2.330330
H -1.949737 2.675692 1.056370
O 2.774995 1.450561 -0.387571
S 2.947601 0.089073 0.266212
O 3.160640 -0.949427 -0.767054
O 3.934925 0.117230 1.340127
O 1.563705 -0.212684 0.955012
O -3.346415 -1.354698 0.151970
C -3.324076 -0.289100 -0.519151
O -2.282918 0.440686 -0.725598
C -4.613130 0.218183 -1.151226
H -4.887422 1.180830 -0.696155
H -4.460221 0.401813 -2.223505
H -5.426788 -0.499930 -1.004363
H -0.276700 4.416101 0.296406
H 1.039988 3.265186 0.585690
H 0.159886 -4.347124 -0.138606
H -1.316829 -3.444961 -0.495862
______
[NiIIIL2(SO4)(OAc)] gas-phase
Total Energy= -3391.3832238 hartree; Dispersion energy= -99.12 kcal/mol
Ni 0.057508 0.561733 -0.000404
N -1.149948 0.046815 -1.499082
N 1.526114 0.275131 -1.255624
N 1.246652 1.114202 1.506390
N -1.425797 0.818104 1.264567
C 0.401268 1.736162 2.543902
C -0.857896 0.896398 2.627387
C 0.967393 0.285629 -2.624727
C -0.309683 -0.524956 -2.583935
C 2.678328 1.206512 -1.115510
C 2.488767 1.868007 1.172101
N 3.290681 1.201058 0.186636
C -2.307131 -0.809949 -1.153501
C -2.503698 -0.183777 1.168301
N -3.103036 -0.137626 -0.148574
H 0.771229 1.329469 -2.913493
H -0.105621 -1.571935 -2.312678
H 2.307355 2.218601 -1.330387
H -1.882472 -1.782646 -0.842360
H 0.926159 1.778814 3.512534
H -1.590978 1.336233 3.322646
H 0.161162 2.761052 2.227122
H -0.617738 -0.124749 2.958240
H 1.691032 -0.150447 -3.332344
H -0.847171 -0.498019 -3.545492
H -2.928257 -0.952087 -2.053881
H 3.422608 0.932513 -1.879203
H 1.469682 0.140289 1.780053
H 1.808883 -0.749112 -1.026309
H -1.488881 0.982793 -1.759614
H -1.753788 1.789109 0.965339
H -3.279980 0.060113 1.912717
H -2.051398 -1.161490 1.416741
H 3.079934 1.996581 2.095034
H 2.173260 2.853682 0.801734
O 1.983901 -2.258489 -0.681658
C 3.812965 -0.095408 0.675833
H 4.396898 0.113682 1.584970
H 2.997341 -0.784438 0.957342
C 4.681740 -0.877253 -0.321729
H 5.707578 -0.481049 -0.344105
H 4.272434 -0.786096 -1.344970
O 4.754254 -2.235727 0.064309
H 3.840987 -2.588483 -0.065189
C -4.531250 -0.444588 -0.190191
H -5.052371 0.229924 0.505831
H -4.907157 -0.214434 -1.198837
C -4.889215 -1.893208 0.152867
H -4.535577 -2.138861 1.172131
H -4.386763 -2.583918 -0.549369
O -6.312064 -1.996459 0.058407
H -6.563404 -2.916600 0.243027
S 0.806127 -2.633312 0.213592
O -0.325042 -3.083442 -0.624323
O 1.209846 -3.546288 1.277480
O 0.379478 -1.296502 0.921396
O -1.770323 3.363659 0.460131
C -0.888815 3.496701 -0.424884
O -0.064003 2.578088 -0.804809
C -0.735380 4.836124 -1.131792
H 0.262998 5.248604 -0.927080
H -0.807993 4.696005 -2.219154
H -1.501341 5.541980 -0.793943
______
Table S2. BP86/TZVP gas-phase optimized Cartesian coordinates
[NiIIIL1(SO4)(OAc)] Total Energy = -3050.94178756 hartree
28 0 -0.26654 0.02162 0.01691
7 0 -0.11272 -1.28585 -1.51723
7 0 0.41061 1.37864 -1.24722
7 0 -0.41209 1.33198 1.55952
7 0 -0.91479 -1.34798 1.30271
6 0 -1.22468 0.67847 2.61196
6 0 -0.80007 -0.77728 2.6687
6 0 0.25163 0.83804 -2.62012
6 0 0.67321 -0.61645 -2.59526
6 0 -0.14321 2.74454 -1.14401
6 0 -0.76953 2.74239 1.32341
6 0 0.08943 3.37194 0.22921
6 0 0.38451 -2.65444 -1.22856
6 0 -0.27841 -2.68339 1.22937
6 0 -0.43403 -3.34086 -0.13964
1 0 -0.8051 0.94433 -2.9157
1 0 1.73659 -0.72073 -2.32183
1 0 -1.21972 2.70036 -1.37787
1 0 1.44195 -2.5465 -0.93368
1 0 -1.0834 1.1749 3.5886
1 0 -1.42592 -1.34851 3.37559
1 0 -2.28477 0.76606 2.32893
1 0 0.25311 -0.85662 2.97792
1 0 0.8744 1.41563 -3.3251
1 0 0.49702 -1.11031 -3.56661
1 0 0.34373 -3.24582 -2.16204
1 0 0.34946 3.36505 -1.91511
1 0 0.59907 1.22029 1.77937
1 0 1.48553 1.39351 -0.98343
1 0 -1.10361 -1.31957 -1.79589
1 0 -1.94232 -1.38739 1.02106
1 0 -0.73871 -3.32412 2.004
1 0 0.78754 -2.54983 1.47079
1 0 -0.65425 3.30699 2.26743
1 0 -1.83404 2.7717 1.04096
8 0 2.90863 1.31448 -0.50326
16 0 3.03164 -0.05075 0.23349
8 0 3.18758 -1.17596 -0.76836
8 0 4.03094 -0.01715 1.34124
8 0 1.58421 -0.25024 0.9485
8 0 -3.46921 -1.07848 0.40045
6 0 -3.36876 -0.13448 -0.42959
8 0 -2.26394 0.44699 -0.76821
6 0 -4.6336 0.40705 -1.09055
1 0 -4.93646 1.33304 -0.5766
1 0 -4.44826 0.6616 -2.14293
1 0 -5.45144 -0.31906 -1.0083
1 0 -0.16379 4.44207 0.16939
1 0 1.15901 3.3095 0.49168
1 0 -0.07913 -4.38015 -0.05737
1 0 -1.50134 -3.39745 -0.41944
------
[NiIIIL2(SO4)(OAc)] Total energy =-3391.070025 hartree
28 0.04207 0.54657 0.01075
7 -1.16288 -0.00086 -1.4961
7 1.5272 0.28624 -1.25282
7 1.23834 1.11539 1.52125
7 -1.4492 0.77953 1.29352
6 0.38377 1.7086 2.57761
6 -0.86847 0.85075 2.65973
6 0.96118 0.27812 -2.62762
6 -0.30856 -0.55365 -2.58837
6 2.65719 1.2614 -1.11531
6 2.46495 1.90907 1.18552
7 3.28429 1.2804 0.18328
6 -2.30814 -0.88292 -1.1386
6 -2.52325 -0.24038 1.1924
7 -3.1136 -0.21539 -0.1325
1 0.74812 1.31869 -2.91917
1 -0.09057 -1.60201 -2.32837
1 2.2475 2.26027 -1.32776
1 -1.86537 -1.84787 -0.82417
1 0.91353 1.744 3.54558
1 -1.60071 1.27879 3.36556
1 0.12598 2.73539 2.2784
1 -0.61643 -0.17178 2.97934
1 1.69056 -0.14926 -3.33677
1 -0.84494 -0.5246 -3.55242
1 -2.93129 -1.04195 -2.03615
1 3.40545 1.01491 -1.88617
1 1.4856 0.14214 1.78424
1 1.85436 -0.71969 -1.01736
1 -1.5255 0.92644 -1.76057
1 -1.79312 1.74881 1.01412
1 -3.30884 0.00129 1.9295
1 -2.05908 -1.21019 1.45277
1 3.05973 2.04491 2.10629
1 2.11967 2.89133 0.82935
8 2.13454 -2.24698 -0.62222
6 3.90745 0.01933 0.66624
1 4.49369 0.27654 1.56301
1 3.14418 -0.72143 0.96699
6 4.81491 -0.71242 -0.34403
1 5.82333 -0.27176 -0.35801
1 4.40688 -0.62537 -1.36935
8 4.95341 -2.07553 0.02383
1 4.05439 -2.4697 -0.09114
6 -4.55601 -0.46758 -0.19815
1 -5.06236 0.23079 0.48668
1 -4.90564 -0.22372 -1.21412
6 -4.99064 -1.90067 0.13847
1 -4.6795 -2.16036 1.16928
1 -4.502 -2.61564 -0.55088
8 -6.41794 -1.93452 0.00223
1 -6.71869 -2.84037 0.1879
16 0.89483 -2.68391 0.22543
8 -0.21027 -3.1505 -0.69617
8 1.267 -3.61164 1.33253
8 0.38907 -1.31477 0.93489
8 -1.81396 3.36209 0.51482
6 -0.97996 3.48527 -0.41902
8 -0.1595 2.56208 -0.81489
6 -0.88913 4.80916 -1.17322
1 0.11951 5.23506 -1.06296
1 -1.05098 4.6415 -2.24835
1 -1.63239 5.51993 -0.79373