H2BDPPA was deprotonated by 2.5 equiv of sodium hydride, and subsequently
NH2
complex of Ni2(BDPPA)2 (3). The molecular structure of 3 was determined by X-ray crystallography as Fig. 3-14.
Fig. 3-14 ORTEP diagrams of Ni2(BDPPA)2 (3). Thermal ellipsoid representation of 3 at probability level. Hydrogen atoms and solvent molecules are omitted for clarity.
The crystals of complex 3 are red, and the crystal system belongs to trigonal, space group is P32. Its lattice constants are a = 16.486(2) Å, b = 16.486(2) Å, c = 32.156(4) Å, α = 90º, β = 90º, γ = 120º. Every unit cell has three molecules (Z=3), R1
= 0.0828, wR2 = 0.1806. The selected bond distances and angles of 3 are listed in Table 3-7, see appendix B for other data.
Table 3-7 Selected bond distances and angles for complex 3.
N(2)-Ni(1)-N(1) 172.9(3) N(4)-Ni(2)-N(5) 174.8(3)
Due to the flexibility of (CH2)3 chains, the structure of complex 3 does have the rigid property of Ni(BDPP). Complex 3 shows a dimeric structure of four-coordinate NiII complex, which has two ligands and two nickel centers staggered to each other.
Each nickel center is coordinated by one arm of each ligands, and it reveals that the geometry of 3 is square-planar.
Because the structure of complex 3 is quite different to Ni(BDPP), the the UV-vis spectrum of 3 is totally different from Ni(BDPP). The UV-vis spectrum of 3 displayed a characteristic absorption band at 460 (ε = 160 M-1cm-1) and a d-d transition band at 650 (ε = 25 M-1cm-1). The UV-vis spectra of 3 is shown in Fig.
3-15.
Fig. 3-15 UV-vis spectrum of 3.
However, in the cyclic voltammogram, complex 3 possesses a quasi-reversible wave with an E1/2 value of 591 mV versus Ag/AgCl in DCM (Fig. 3-16). Moreover, this redox wave will be decreased with the scan times increasing, exposed that complex 3 could be oxidized to NiIII species, the NiIII species is considerably unstable.
3.4 Synthesis and Discussion of NiIII2(BDPPA)2(BF4)2 (5)
From the electrochemical evidence of complex 3, which shows its potential of forming an nickel(III) species. The redox potential of 3, however, is higher than ferrocenium salt (Fc+/Fc, 467 mV vs Ag/AgCl in DCM). Thus, we synthesized a derivative of ferrocenium salt, 1,1’-dibromoferrocenium tetrafluoroborane (Fc+/Fc, 797 mV vs Ag/AgCl in DCM) as oxidant to oxidized complex 3 to [NiIII2(BDPPA)2](BF4)2 (5). Complex 5 can be characterized by UV-vis spectroscopy and electron paramagnetic resonance spectroscopy (EPR). In addition, DFT calculation results could provide some possibilities of the geometric and electronic structure of this NiIII complex.
The UV-vis spectrum of the formation of NiIII2(BDPPA)2(BF4)2 can be shown by adding 2 equiv 1,1-dibromoferroceium tetrafluoroborate to complex 3 at –40 °C.
Complex 5 displayed three characteristic absorption bands at 300, 335, and 570 nm (ε
= 11035, 5200, and 3255 M-1cm-1) (Fig. 3-17).
Fig. 3-17 UV-vis spectrum of the formation of 5.
The electron configuration of the nickel center in complex 5 is d7, thus a NiIII signal will be found in EPR spectroscopy. The EPR spectrum of 5 in ACN at 77K exhibited a rhombic signal (gx = 2.182, gy = 2.136, and gz = 2.073) with several super-hyperfine triplet (Ayy = 67.8 G, Ayz = 26.04 G) (Fig. 3-18). The significant super-hyperfine coupling (from EPR simulation data) shows that the unpaired electrons of both nickel(III) center could overlap with the nitrogen atoms on the equatorial plane by the dyz and dz2 orbitals in each nickel center. These results inferred that the axial nitrogen might not be able to ligate to nickel center when the complex oxidized to a nickel(III) species.
Fig. 3-18 The EPR spectra and simulate diagram of 5.
DFT calculation of 5 was performed to gain insight into the geometric and
calculation employed the Gaussian 09 (G09) program packagein B3LYP level with a mixed basis set comprised of 6-31 g for C, H; 6-31g+(d) for N, O and the Hay-Wadt relativistic effective core potentials (LANL08)for the Ni atom was performed.
The geometry for the optimized structure of 5 has two hypotheses, either the axial donor has bound to nickel center to form a five coordinate square pyramidal when it oxidized to nickel (III) species, or the nickel(III) species remains a square planer geometry. The spin density plots are shown in Fig. 3-19. According to these results, we can found that in the non-bonding case, the unpaired electrons were complicatedly located on the dxz orbitals of each NiIII, and these orbitals have strong overlaps with the pz orbital of the equatorial nitrogen atoms of the pyrrolidine. But in the bonding case, the unpaired electrons were separated concentrated on two nickel centers—the dz2 orbital of NiIII and coupled to the pz orbital of the axial nitrogen atom of aniline and the dxz orbital of NiIII just like the nickel center of non-bonding case.
From the DFT calculation results, we can observed the potential energy of the axial nitrogen non-bounding to nickel center case is lower than the bounding case for 23.2 kcal/mol. Thus, from the ERP and DFT results, we could conclude that the axial nitrogen atom could not bind to the nickel(III) center while it oxidized to nickel(III).
The nickel(III) species with square planer geometry are quite rare in the literature.23c
Fig. 3-19 The spin density population of 5 by computation. (Left: Non-bonding, Right: Bonding.)
Meanwhile, the comparison of orbital and atomic contribution of the non-bonding and bonding cases are also shown below.
Table 3-8 Orbital and atomic contribution to the spin density of complex 5 (Non-bonding).
Ni1 Ni2
Ni
dz2 0.032 0.036
dx2-y2 0.090 0.093
dxz -0.002 0.603
dyz 0.616 -0.016
dxy 0.024 0.015
N1 -0.042 -0.023
N2 -0.039 -0.024
N3 (Aniline) 0.000 0.003
O1 0.220 0.214
Table 3-9 Orbital and atomic contribution to the spin density of complex 5 (Bonding).
Ni1 Ni2
Ni
dz2 0.751 0.090
dx2-y2 0.302 0.081
dxz 0.029 0.490
dyz 0.027 0.021
dxy 0.041 0.062
N1 -0.062 -0.045
N2 -0.025 -0.029
N3 (Aniline) 0.273 0.010
O1 -0.050 0.284
O2 -0.014 0.145
3.5 Discussion between Nickel-complexes and Superoxide 3.5.1 [NiIII(BDPMeP)](BF4) (4)
In order to test the capability of complex 4 toward the oxidation of superoxide, complex 4 was reacted with KO2. A rapid color change of the solution from brown to green accompany with some bubbles formation. According to our previous study, the formation bubbles could be O2. Besides, after the resulting solution was filtered, the solvent of green filtrate was removed under vacuum and afforded a green solid residue. This green residue could be recrystallized by slow diffusion (DCM/pentane) at room temperature to obtain complex 1. The reaction could be monitored by UV-vis spectroscopy and the formation gas during the reaction could be detected by using Milli-Whistle GC to have a quantitative and qualitative analysis.
The reaction of complex 4 and KO2 was performed by adding 3 mL ACN solution of [NiIII(BDPMeP)](BF4)(4) (1.5 × 10-4 M) to KO2 powder (0.0070 g, 50 equiv) in a quartz cell and was detected by UV-vis spectroscopy. Complex 4 has three characteristic absorption bands at 300, 375, and 455 nm. When it reacted with KO2, these three characteristic absorption bands were decreased, and a new characteristic absorption band at 360 nm was exhibited. After 21 min, there was only a characteristic absorption band at 360 nm in the final spectrum, indicating the formation of complex 1.
Fig. 3-20 UV-vis spectrum of the reaction between 4 and KO2.
In addition, the Milli-Whistle GC could be performed to analyze the formed gas form the reaction. We can infer that the reaction sample of complex 4 can generate 1.125 mL O2(g) more than blank experiment. The generated amount of O2 is about 92% yield. These experiment show that complex 4 can be reduced to complex 1 and oxidized O2− into O2, imitating the function of NiSODox successfully.
Fig. 3-21 GC spectrum of the reaction between 4 and KO2. (a) The calibration line of the amount of O and its frequency (b) Blank (c) Sample (Complex 4)
3.5.2 NiIII2(BDPPA)2(BF4)2 (5)
Since complex 5 reacted with KO2, the color of the solution changed from dark purple to yellow accompany with some bubbles formation. Besides, after the resulting solution was filtered, the solvent of yellow filtrate was removed under vacuum and recrystallized by layer (THF/hex) at room temperature. Pink crystals were obtained over three days. X-ray crystallographic analysis shows those crystals are Ni2(BDPPA)2 (3). The reaction of complex 4 and KO2 could be monitored and analyzed by UV-vis spectroscopy and Milli-Whistle GC, respectively.
The preparation of the reaction solution of complex 5 and KO2 is the same method as the reaction of 4 and KO2. By adding 3-mL THF solution of NiIII2(BDPPA)2(BF4)2 (5) (1.0 × 10-3 M) to KO2 powder (0.0053 g, 50 equiv) in a quartz cell and then detected by UV-vis spectroscopy, the initial spectrum of complex 5 having a characteristic absorption band at 570 nm was decayed and a characteristic absorption band at 425 nm was formed. The 425 nm absorption band could be inferred to the characteristic absorption band of complex 4, yet it shifted slightly because of the possibilities of the different solvent effect or influenced by the formation of byproduct.
Fig. 3-22 UV-vis spectrum of the reaction between 5 and KO2.
From Milli-Whistle GC analyzations, it reveals that, 0.402 mL O2(g) was generated in the reaction sample more than that of blank experiment. The O2
formation is 82% yield. These results revealed that although complex 5 can not demonstrated the dissociation and association of the axial donor toward NiSOD, but can be performed the function of oxidizing O2− into O2, and complex 5 itself is reduced to complex 3 straightforwardly.
Fig. 3-23 GC spectrum of the reaction between 5 and KO2. (a) The calibration line of the amount of O2(g) and its frequency (b) Blank (c) Sample (Complex 5)
CHAPTER FOUR: CONCLUDING REMARKS
In this study, Ni(BDPMeP) (1) and Ni2(BDPPA)2 (3) have been designed and synthesized for the active site of NiSOD, based on the skeleton of Ni(BDPP). From the electron donating abilities and reactivities of 1 and 3, we could learn more about the modification methods for the mimics of NiSOD.
First, complex 1 was synthesized from H2(BDPMeP), which was modulated the side-arms of H2BDPP by altering phenyl group to the tolyl group. The chemical property of 1 was similar to Ni(BDPP), however, with the para-position of benzene ring modification of electron-rich methyl group, the redox potential could be improve to 250 mV vs Ag/AgCl. From literature, this negative redox potential could increase the catalytic efficient of superoxide disproportionation reaction. Besides, DFT calculation results demonstrated that with the electron-rich methyl group, the unpaired electron could be more concentrated on the nickel center than [NiIII(BDPP)]·(PF6). In addition, [NiIII(BDPMeP)](BF4) (4) could be obtained by the oxidation of 1, similar to [NiIII(BDPP)]·(PF6), 4 reveals that it can perform the superoxide oxidation reactivity by reducing to 1, and imitate the function of NiSODox.
Second, H2BDPPA, was modified from the linker of H2BDPP by introducing aniline as the axial coordination group to replace pyridinyl group. With the axial group modification and the flexible long CH2 chains of H2BDPPA, a dimer complex, Ni2(BDPPA)2 (3), have been obtained. Ni2(BDPPA)2 could be oxidized to nickel(III)
four-coordination environment, rather than five-coordination complex. Complex 5 presented the function of oxidizing O2− into O2, and complex itself is reduced to 3 straightforwardly.
In conclusion, nickel(III) complexes, 4 and 5, could demonstrate the ability to convert O2– into O2, just like the oxidized form of NiSOD. Further investigation will focus on the improvement of the capability of the nickel mimic towards the reduction of O2- into H2O2. Besides, a series of derivatives of H2BDPPA will be synthesized by adding a substituted hydrophilic group in the para-position to enhance its hydrophilicity and water solubility. Thus, with the enhancement of SOD activity available, the medicinal applications of these mimics could be improve in the future.
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Appendix A Spectra of NMR
N BrBrOH
1 H-NMR spectrum of 2,6-Bis(bromomethyl)pyridine
N
OOEt O OMe
1 H-NMR spectrum of (S)-Ν-Ethoxycarbonylproline methyl ester
N
OOEt OH
1 H-NMR spectrum of (S)-2-(Bis(4-methylphenyl)hydroxymethyl)-N-ethoxycarbonylpyrrolidine
OH
1 H-NMR spectrum of (S)-2-(Bis(4-methylphenyl)hydroxymethyl)pyrrolidine
1 H-NMR spectrum of 2,6-Bis(((S)-2-(bis(4-methylphenyl)hydroxymethyl)-1-pyrrolidinyl)methyl)- pyridine N NOH NOH
N NOH N
13 C-NMR spectrum of 2,6-Bis(((S)-2-(bis(4-methylphenyl)hydroxymethyl)-1-pyrrolidinyl)methyl)- pyridine
NOHHO
1 H-NMR spectrum of N-benzylbis(3-hydroxylpropyl)amine
NBrBr
1 H-NMR spectrum of N-benzylbis(3- bromopropyl)amine
1 H-NMR spectrum of (S)-2-(Diphenylhydroxymethyl)-N-ethoxycarbonylpyrrolidine N
OOEt OH
H N
OH
1 H-NMR spectrum of (S)-2-(Diphenylhydroxymethyl)pyrrolidine
1 H-NMR spectrum of (S)-2-(Diphenylhydroxymethyl)pyrrolidine NNOHN
NNOH
13 C-NMR spectrum of (S)-2-(Diphenylhydroxymethyl)pyrrolidine
FeII BrBr
1 H-NMR spectrum of 1,1’-Dibromoferrocene
Appendix B X-ray Crystal Data and Structure Refinement
NiBDPMeP (1)
Table B-1 Crystal data and structure refinement for NiBDPMeP (1)
Identification code 14685
Empirical formula C45 H49 N3 Ni O2
Formula weight 722.58
Temperature 200(2) K
Wavelength 0.71073 Å
Crystal system Orthorhombic
Space group P 21 21 2
Density (calculated) 1.146 Mg/m3
Absorption coefficient 0.501 mm-1
F(000) 768
Crystal size 0.72 x 0.16 x 0.04 mm3
Theta range for data collection 1.55 to 25.08°.
Index ranges -23<=h<=22, -9<=k<=9, -15<=l<=15
Reflections collected 11694
Independent reflections 3662 [R(int) = 0.0599]
Completeness to theta = 25.08° 99.0 %
Absorption correction multi-scan
Max. and min. transmission 0.9802 and 0.7144
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 3662 / 0 / 232
Goodness-of-fit on F2 1.064
Final R indices [I>2sigma(I)] R1 = 0.0589, wR2 = 0.1579
R indices (all data) R1 = 0.0824, wR2 = 0.1674
Absolute structure parameter 0.04(3)
Bond lengths [Å] and angles [°] for NiBDPMeP (1)
N(1)-C(1)-H(1A) 111.3
N(1)-C(18)-H(18A) 109.2
Symmetry transformations used to generate equivalent atoms:
[NiHBDPMeP](ClO4)·(CH2Cl2)2 (2)
Table B-2 Crystal data and structure refinement for [NiHBDPMeP](ClO4)·(CH2Cl2)2
(2)
Identification code ch14644
Empirical formula C47 H54 Cl5 N3 Ni O6
Formula weight 992.89
Temperature 200(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group C 2
Density (calculated) 1.390 Mg/m3
Absorption coefficient 0.741 mm-1
F(000) 2072
Crystal size 0.78 x 0.72 x 0.56 mm3
Theta range for data collection 0.99 to 25.05°.
Index ranges -45<=h<=48, -11<=k<=12, -12<=l<=9
Reflections collected 16560
Independent reflections 7838 [R(int) = 0.0243]
Completeness to theta = 25.05° 99.6 %
Absorption correction multi-scan
Max. and min. transmission 0.6817 and 0.5957
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 7838 / 1 / 560
Goodness-of-fit on F2 1.040
Final R indices [I>2sigma(I)] R1 = 0.0478, wR2 = 0.1354
R indices (all data) R1 = 0.0558, wR2 = 0.1515
Absolute structure parameter 0.018(14) Largest diff. peak and hole 0.542 and -0.617 e.Å-3
Bond lengths [Å] and angles [°] for[NiHBDPMeP](ClO4)·(CH2Cl2)2 (2)
C(27)-C(28) 1.521(7)
O(6)-Cl(1) 1.428(5)
C(18)-C(17)-H(17B) 111.2
O(2)-C(31)-C(32) 107.6(3)
Cl(5)-C(47)-H(47A) 109.9
Symmetry transformations used to generate equivalent atoms:
NiBDPPA (3)
Table B-3 Crystal data and structure refinement for NiBDPPA (3)
Identification code a13606
Empirical formula C93 H104 Cl2 N6 Ni2 O4
Formula weight 1558.14
Temperature 200(2) K
Wavelength 0.71073 Å
Crystal system Trigonal
Space group P 32
Density (calculated) 1.026 Mg/m3
Absorption coefficient 0.471 mm-1
F(000) 2478
Crystal size 0.24 x 0.16 x 0.08 mm3
Theta range for data collection 1.90 to 25.03°.
Index ranges -13<=h<=19, -19<=k<=15, -38<=l<=38
Reflections collected 32090
Independent reflections 15845 [R(int) = 0.0709]
Completeness to theta = 25.03° 97.8 %
Absorption correction multi-scan
Max. and min. transmission 0.9633 and 0.8954
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 15845 / 1 / 924
Goodness-of-fit on F2 0.859
Final R indices [I>2sigma(I)] R1 = 0.0828, wR2 = 0.1806
R indices (all data) R1 = 0.1725, wR2 = 0.2111
Absolute structure parameter 0.147(19)
Largest diff. peak and hole 0.313 and -0.451 e.Å-3
Bond lengths [Å] and angles [°] for NiBDPPA (3)
C(29)-H(29) 0.9500
C(54)-C(55) 1.411(14)
C(84)-C(89) 1.341(14)
C(10)-C(11)-H(11) 116.5
C(27)-C(28)-H(28) 121.0
C(38)-C(43)-H(43) 118.0
C(56)-C(57)-H(57) 120.5
C(64)-C(77)-H(77) 109.9
H(91A)-C(91)-H(91B) 108.2
Symmetry transformations used to generate equivalent atoms: