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1.
One-bond heteronuclear spin-spin coupling constants (1)J(PX) (X=H, O, S, Se, C and N) between the phosphorus atom and axial and equatorial substituents in dioxaphosphorinanes are computed using density functional theory (DFT). The experimental values of these coupling constants for a variety of substituents can be applied to identify different diastereoisomers. The DFT calculations confirm the systematic trend observed in experiment, and indicate that the computed (1)J(PX) coupling constants are related to the length of the axial and equatorial bonds. A similar relation between the phosphorus chemical shift and the R(PX) bond length appears to be valid, with the exception of selenium substituents.  相似文献   

2.
An ab initio study has been carried out to determine the structures, relative stabilities, and spin-spin coupling constants of a set of 17 methyl-substituted 1,3-diborata-2,4-diphosphoniocyclobutanes B(2)P(2)(CH(3))(n)H(8-n), for n = 0, 1, 2, 4, with four-member B-P-B-P rings. The B-P-B-P rings are puckered in a butterfly conformation, in agreement with experimental data for related molecules. Isomers with the CH(3) group bonded to P are more stable than those with CH(3) bonded to B. If there is only one methyl group or if two methyl groups are bonded to two different P or B atoms, isomers with equatorial bonds are more stable than those with axial bonds. However, when two methyl groups are present, the gem isomers are the most stable for molecules B(2)P(2)(CH(3))(2)H(6) with P-C and B-C bonds, respectively. Transition structures present barriers to the interconversion of two equilibrium structures or to the interchange of axial and equatorial positions in the same isomer. These barriers are very low for the isomer with two methyl groups bonded to B in axial positions for the isomer with four axial bonds and for the isomer with geminal B-C bonds at both B atoms. Coupling constants (1)J(B-P), (1)J(P-C), (1)J(B-C), (2)J(P-P), and (3)J(P-C) are capable of providing structural information. They are sensitive to the number of methyl groups present and can discriminate between axial, equatorial, and geminal bonds, although not all do this to the same extent. The one-bond coupling constants (1)J(B-P), (1)J(P-C), and (1)J(B-C) are similar in equilibrium and transition structures, but (3)J(P-C) and (2)J(P-P) are not. These coupling constants and those of the corresponding fluoro-derivatives of the 1,3-diborata-2,4-diphosphoniocyclobutanes demonstrate the great sensitivity of phosphorus coupling to structural and electronic effects.  相似文献   

3.
Stereoelectronic effects proposed for C-H bonds in cyclohexane, 1, 3-dioxane, 1,3-oxathiane, and 1,3-dithiane were studied computationally. The balance of three effects, namely, sigma(C)(-)(X) --> sigma(C)(-)(H)()eq, sigma(C)(-)(H)()eq --> sigma(C)(-)(X), and n(p)(X) --> sigma(C)(-)(H)()eq interactions, was necessary to explain the relative elongation of equatorial C(5)-H bonds. The role of homoanomeric n(p) --> sigma(C(5))(-)(H)()eq interaction is especially important in dioxane. In dithiane, distortion of the ring by long C-S bonds dramatically increases overlap of sigma(C(5))(-)(H)()eq and sigma(C)(-)(S) orbitals and energy of the corresponding hyperconjugative interaction. Anomeric n(p)(X) --> sigma(C)(-)(H)()ax interactions with participation of axial C-H bonds dominate at C(2), C(4), and C(6). The balance of hyperconjugative interactions involving C-H(ax) and C-H(eq) bonds agrees well with the relative bond lengths for all C-H(ax)/C-H(eq) pairs in all studied compounds. At the same time, the order of one-bond spin-spin coupling constants does not correlate with the balance of stereoelectronic effects in dithiane and oxathiane displaying genuine reverse Perlin effect.  相似文献   

4.
The ability of the equatorial C‐H bonds to form C‐H—O hydrogen bonds was studied by measuring the high‐pressure Raman spectra. We have investigated the effect of pressure versus C‐H—O interactions in 1,3‐dioxane/D2O mixtures. Dilution of 1,3‐dioxane leads to a shift of the C‐H signals to higher frequencies under ambient pressure. Based on the pressure‐dependence of the Raman spectra, we have found that the equatorial C‐H groups of 1,3‐dioxane displays a remarkably different ability to serve as the weak hydrogen bond donors in comparison to the axial C‐H of 1,3‐dioxane. The new Raman spectral features observed under high pressure may arise from the combined effect of hydrogen‐bond network changes, hydrogen bond‐like C‐H—O interactions formation, cluster size changes, etc. This finding may be important to diastereo‐ and enantioselective synthesis.  相似文献   

5.
The N-H...X (X = N,O,S) intramolecular hydrogen bond in the series of 2(2'-heteroaryl)pyrroles and their trifluoroacetyl derivatives is examined by the (1)H, (13)C, (15)N spectroscopy and density functional theory (DFT) calculations. The influence of the hydrogen bond on coupling and shielding constants is considered. It is shown that the N-H...N intramolecular hydrogen bond causes a larger increase in the absolute size of the (1)J(N,H) coupling constant and a larger deshielding of the bridge proton than the N-H...O hydrogen bond. The effect of the N-H...S interaction on the (1)J(N,H) coupling constant and the shielding of the bridge proton is small. The NMR parameter changes in the series of the 2(2'-heteroaryl)pyrroles due to N-H...X hydrogen bond and the series of the 1-vinyl-2-(2'-heteroaryl)-pyrroles due to C-H...X hydrogen bond have the same order. The proximity of the nitrogen, oxygen or sulfur lone pair to the F...H hydrogen bridge quenches the trans-hydrogen bond spin-spin couplings (1h)J(F,H-1) and (2h)J(F,N).  相似文献   

6.
Structural and energetic consequences of homoanomeric n(X) --> beta-sigma(C-Y) interactions in saturated six-membered heterocycles where X = O, N, S, Se and Y = H, Cl were studied computationally using a combination of density functional theory (B3LYP) and Natural Bond Orbital (NBO) analysis. Unlike the classic anomeric effect where the interacting donor and acceptor orbitals are parallel and overlap sidewise in a pi-fashion, orbital interactions responsible for homoanomeric effects can follow different patterns imposed by the geometric restraints of the respective cyclic moieties. For the equatorial beta-C-Y bonds in oxa-, thia- and selena-cyclohexanes, only the homoanomeric n(X)(ax) --> sigma(C-Y)(eq) interaction (the Plough effect) with the axial lone pair of X is important, whereas the n(X)(eq) --> sigma(C-Y)(eq) interaction (the W-effect) is negligible. On the other hand, the W-effect is noticeably larger than the n(X)(ax) --> sigma(C-Y)(eq) interaction in azacyclohexanes. Hyperconjugation is a controlling factor which determines relative trends in the equatorial beta-C-H bonds in heterocycloxanes. In contrast, all homoanomeric interactions are weak for the respective axial bonds where relative lengths are determined by intramolecular electron transfer through exchange interactions and polarization-induced rehybridization. Although the homoanomeric effects are considerably weaker than the classic vicinal anomeric n(X)(ax)-->alpha-sigma(C-Y)(ax) interactions, their importance increases significantly when the acceptor ability of sigmaorbitals increases as a result of bond stretching and/or polarization. Depending on the number of electrons and the topology of interactions, homoconjugation interactions can be cooperative (enhance each other) or anticooperative (compete with each other). Such effects reflect symmetry of the wave function and can be considered as weak manifestations of sigma homoaromaticity or homoantiaromaticity.  相似文献   

7.
The exceptional stability of recently reported pentaorganosilicates is investigated by bond energy analyses. Experimental coupling constants are used to probe their electronic structure, entailing bonds with mixed ionic-covalent character. Our analyses reconfirm that the axial bonds are more prone to heterolytic cleavage than are the equatorial bonds. Aryl substituents provide substantial electronic stabilization by charge delocalization, but cause steric crowding due to ortho-hydrogen repulsion. In contrast, silicates with two ax,eq biaryl groups are not congested. The remaining substituent is confined to an equatorial site, where it is insensitive to elimination. These concepts adequately explain the experimentally observed stability trends and are valuable for designing other stable pentaorganosilicates.  相似文献   

8.
Theoretical and experimental 2JHH coupling constants for six-membered rings containing oxygen or sulfur atoms were studied to investigate whether the 2JHH coupling constant can be used for stereoelectronic studies in heterocyclohexanes, instead of 1JCH, because it is well known that experimental measurements of 2JHH coupling constants at low temperature are much easier to determine than the corresponding 1JCH couplings. For all compounds studied here, the 2JHH coupling constants are affected by sigma*C-H antibonding occupancy together with bond angle effects. For cyclohexane and oxygen-containing compounds, the influence on the geminal coupling for Hax-C2-Heq and for X1-C2-X3 (X=O and C), bond angles are more pronounced than for the sulfur derivatives.  相似文献   

9.
Density functional theory calculations are used to compute proton nuclear magnetic resonance (NMR) chemical shifts, interatomic distances, atom–atom interaction energies, and atomic charges for partial structures and conformers of α‐D‐glucopyranose, β‐D‐glucopyranose, and α‐D‐galactopyranose built up by introducing OH groups into 2‐methyltetrahydropyran stepwisely. For the counterclockwise conformers, the most marked effects on the NMR shift and the charge on the OH1 proton are produced by OH2, those of OH3 and OH4 being somewhat smaller. This argues for a diminishing cooperative effect. The effect of OH6 depends on the configuration of the hydroxymethyl group and the position, axial or equatorial, of OH4, which controls hydrogen bonding in the 1,3‐diol motif. Variations in the interaction energies reveal that a “new” hydrogen bond is sometimes formed at the expense of a preexisting one, probably due to geometrical constraints. Whereas previous work showed that complexing a conformer with pyridine affects only the nearest neighbour, successive OH groups increase the interaction energy of the N⋯H1 hydrogen bond and reduce its length. Analogous results are obtained for the clockwise conformers. The interaction energies for C―H⋯OH hydrogen bonding between axial CH protons and OH groups in certain conformers are much smaller than for O―H⋯OH bonds but they are largely covalent, whereas those of the latter are predominantly coulombic. These interactions are modified by complexation with pyridine in the same way as O―H⋯OH interactions: the computed NMR shifts of the CH protons increase, the atom–atom distances are shorter, and interaction energies are enhanced.  相似文献   

10.
Theoretical analysis within the frame of the Topological Theory of Atoms in Molecules confirms the repulsive steric interaction between an axial dimethylphosphinoyl group and the syn-diaxial hydrogens in cyclohexane derivative 2-ax. In seemingly good agreement with experiment, equatorial isomer 2-eq was calculated to be 1.49 kcal/mol more stable than 2-ax. (Experimental energy difference in (diphenylphosphinoyl)cyclohexane, Delta H(o) = 1.96 kcal/mol.) In contrast, axial 2-(dimethylphosphinoyl)-1,3,5-trithiane, 3-ax, was calculated to be 6.38 kcal/mol more stable than 3-eq. (Experimentally, the axial conformer of 2-(diphenylphosphinoyl)-1,3,5-trithiane, was found to be 1.43 kcal/mol more stable than the equatorial conformer, in solvent chloroform.) Theoretical analysis, in particular the electron density at the bond critical point within the C(4,6)-H...O=P bonding trajectory, implies significant bonding in this segment of interacting atoms. By the same token, substantial positive charge is acquired by the C--H bonds adjacent to the sulfonyl groups in disulfone 4. Hydrogen bonding between the phosphoryl group and H(4,6) leads to stabilization of 4-ax, which is estimated to be 5.0 kcal/mol lower in energy than 4-eq. This conclusion is supported by examination of P==O...H--C(4,6) bond trajectories, as well as from evaluation of the critical point properties along those interacting moieties. By contrast, fluorinated derivative 5 is more stable in the equatorial conformation, indicating a repulsive electrostatic interaction of the C--F...O-P entity in 5-ax.  相似文献   

11.
According to the (1)H, (13)C and (15)N NMR spectroscopic data and ab initio calculations, the strong N--H...O intramolecular hydrogen bond in the Z-isomers of 2-(2-acylethenyl)pyrroles causes the decrease in the absolute size of the (1)J(N,H) coupling constant by 2 Hz in CDCl(3) and by 4.5 Hz in DMSO-d(6), the deshielding of the proton and nitrogen by 5-6 and 15 ppm, respectively, and the lengthening of the N--H link by 0.025 A. The N--H...N intramolecular hydrogen bond in the 2(2'-pyridyl)pyrrole leads to the increase of the (1)J(N,H) coupling constant by 3 Hz, the deshielding of the proton by 1.5 ppm and the lengthening of the N--H link by 0.004 A. The C--H...N intramolecular hydrogen bond in the 1-vinyl-2-(2'-pyridyl)-pyrrole results in the increase of the (1)J(C,H) coupling constant by 5 Hz, the deshielding of the proton by 1 ppm and the shortening of the C--H link by 0.003 A. Different behavior of the coupling constants and length of the covalent links under the hydrogen bond influence originate from the different nature of the hydrogen bonding (predominantly covalent or electrostatic), which depends in turn on the geometry of the hydrogen bridge. The Fermi-contact mechanism only is responsible for the increase of the coupling constant in the case of the predominantly electrostatic hydrogen bonding, whereas both Fermi-contact and paramagnetic spin-orbital mechanisms bring about the decrease of coupling constant in the case of the predominantly covalent hydrogen bonding.  相似文献   

12.
Theoretical examination [B3LYP/6-31G(d,p), PP/IGLO-III//B3LYP/6-31G(d,p), and NBO methods] of six-membered cyclohexane 1 and carbonyl-, thiocarbonyl-, or methylidene-containing derivatives 2-27 afforded precise structural (in particular, C-H bond distances) and spectroscopic (specifically, one-bond (1)J(C)(-)(H) NMR coupling constants) data that show the consequences of stereoelectronic hyperconjugative effects in these systems. Major observations include the following. (1) sigma(C)(-)(H)(ax)() -->(C)(=)(Y) and pi(C)(=)(Y) --> sigma(C)(-)(H)(ax)() (Y = O, S, or CH(2)) hyperconjugation leads to a shortening (strengthening) of the equatorial C-H bonds adjacent to the pi group. This effect is reflected in smaller (1)J(C)(-)(H)(ax)() coupling constants relative to (1)J(C)(-)(H)(eq)(). (2) Comparison of the structural and spectroscopic consequences of sigma(C)(-)(H)(ax)() --> pi(C)(=)(Y) hyperconjugation in cyclohexanone 2, thiocyclohexanone 3, and methylenecyclohexane 4 suggests a relative order of acceptor orbital ability C=S > C=O > C=CH(2), which is in line with available pK(a) data. (3) Analysis of the structural and spectroscopic data gathered for heterocyclic derivatives 5-12 reveals some additivity of sigma(C)(-)(H)(ax)() --> pi(C)(=)(Y), pi(C)(=)(Y) --> sigma(C)(-)(H)(ax)(), n(X) --> sigma(C)(-)(H)(ax)(), n(beta)(O) --> sigma(C)(-)(H)(eq)(), and sigma(S)(-)(C) --> sigma(C)(-)(H)(eq)() stereoelectronic effects that is, nevertheless, attenuated by saturation effects. (4) Modulation of the C=Y acceptor character of the exocyclic pigroup by conjugation with alpha-heteroatoms O, N, and S in lactones, lactams, and methylidenic analogues 13-24 results in decreased sigma(C)(-)(H)(ax)() --> pi(C)(=)(Y) and pi(C)(=)(Y) --> sigma(C)(-)(H)(ax)() hyperconjugation. (5) Additivity of sigma(C)(-)(H)(ax)() --> pi(C)(=)(Y) and pi(C)(=)(Y) --> sigma(C)(-)(H)(ax)() hyperconjugative effects is also apparent in 1,3-dicarbonyl derivative 25 (C=Y equal to C=O), 1,3-dithiocarbonyl derivative 26 (C=Y equal to C=S), and 1,3-dimethylidenic analogue 27 (C=Y equal to C=CH(2)).  相似文献   

13.
An ab initio study has been carried out to determine the structures, relative stabilities, and spin-spin coupling constants of a set of 15 fluoro-substituted 1,3-diborata-2,4-diphosphoniocyclobutanes B(2)P(2)F(n)H(8-n), for n = 0, 1, 2, 4, with four-member B-P-B-P rings. Except for B(2)P(2)F(4)H(4) with four fluorines bonded to two borons, these rings are puckered in a butterfly conformation. For a fixed number of fluorines, the isomers with B-F bonds are significantly more stable than those with P-F bonds. As the number of fluorines increases, the energy difference between the most stable isomer and the other isomers increases. Transition structures which interconvert axial and equatorial positions present relatively small inversion barriers. Coupling constants involving (31)P, namely, (1)J(B-P), (1)J(P-F), (2)J(P-P), (2)J(P-F), and (3)J(P-F) are large and are capable of providing structural information. They are sensitive to the number of fluorines present and can discriminate between axial, equatorial, and geminal B-F and P-F bonds, although not all do this to the same extent. (1)J(B-P) and (2)J(P-P) are similar in equilibrium and transition structures. Although transition structures no longer discriminate between axial and equatorial bonds, (1)J(P-F) and (3)J(P-F) remain sensitive to the number of fluorine atoms present.  相似文献   

14.
Bis-thiocarbono-hydrazones are found to be a class of sensitive, selective, ratiometric, and colorimetric chemosensors for anions such as fluoride (F(-)) or acetate (Ac(-)). The sensitivities, or the binding constants of the sensors with anions, were found to be strongly dependent on the substituents appended on the pi-conjugation framework, the delocalization bridge CH==N, the aromatic moiety, and the hetero atom in the C==X group (X=O, S) of the sensors. Single-crystal structures and (1)H NMR titration analysis shows that the --CH==N-- moiety is a hydrogen-bond donor, and it is proposed that an additional CHF hydrogen bond is formed for the sensors in the presence F(-). A sensor bearing anthracenyl groups is demonstrated as a switch-on fluorescent chemosensor for F(-) and Ac(-). The recognition of F(-) in acetonitrile (MeCN) by a sensor with nitrophenyl substituents is tolerant to MeOH (MeCN/MeOH=10:1, v/v) and water (MeCN/H(2)O=30:1, v/v); at these solvent ratios the absorption intensity of the sensor-F(-) complex solution at maximal absorption wavelength was attenuated to half of the original value in pure MeCN.  相似文献   

15.
The structure, vibrational force constants and infrared and Raman intensities have been calculated for 1,3,5-trioxane using a 3-21G basis set. These results have been used to identify some possible inaccuracies in experimental diffraction based structures and in vibrational assignments. It is demonstrated that there is a marked contrast between the trends in the vibrational force constants and in the King's effective atomic charges of the axial and equatorial CH bonds in the series cyclohexane, 1,4-dioxane and 1,3,5-trioxane. The axial CH stretching force constant decreases by 0.04 mdyne Å−1 for each adjacent oxygen atom, whereas that of the equatorial CH bond increases by 0.15 mdyne Å−1 per oxygen. In trioxane the effective atomic charge of the axial hydrogen is twice that of the equatorial. Atomic polar tensors are calculated in a bond oriented frame, and the effect of the oxygens on CH stretching and bending mode intensities discussed. Some properties are also calculated using the 4-31G basis.  相似文献   

16.
Primary kinetic isotope effects (KIE) have been determined spectrophotometrically for the reaction of NAD(+) analogues (pyridinium, quinolinium, phenanthridinium, and acridinium ions) with 1,3-dimethyl-2-phenylbenzimidazoline in a 4:1 mixture of 2-propanol and water by volume at 25 degrees C. The values of KIE varied systematically from 6.27 to 4.06 as the equilibrium constant changed from around 10 to around 10(12). This is consistent with Marcus theory of atom transfer, assuming that there are no high-energy intermediates. Within this theory, the perpendicular effect is responsible for most of the change in KIE. The Marcus theory of atom transfer is consistent with a linear, triatomic model of the reaction. Perpendicular effects arise from the systematic decrease of bond distances and increase of bond orders in the critical complexes of the two related degenerate hydride transfer reactions as their C--H bonds become stronger. The parallel effect (Leffler--Hammond effect) is attenuated by the fairly high intrinsic barrier (lambda/4 is around 92 kJ/mol) and makes a smaller contribution to the change in the KIE.  相似文献   

17.
An NMR study of the diaxial/diequatorial chair equilibrium in a range of silylated derivatives of trans-1,4- and trans-1,2-dihydroxycyclohexane is reported and discussed with a view to explaining unusually large populations of chair conformations with axial substituents, noted previously for some monosilyloxycyclohexanes and in some silylated sugars. X-ray diffraction studies of three bis-triphenylsilyloxycyclohexanes are reported and show both axial and equatorial silyloxy groups with the exocyclic bonds eclipsed. Eclipsing is also suggested by molecular mechanics (MM3) calculations on such derivatives. Both axial and equatorial tertiary silyl groups have 1,3-repulsive interactions with whatever substituents or hydrogen atoms are at the two adjacent equatorial positions, and these are relieved by rotation toward the eclipsed conformation of the exocyclic C-O bond. The three substituents on silicon interact attractively with the nine atoms at the 3, 4, and 5-positions of the cyclohexane ring and calculations suggest that these stabilizing interactions are significantly greater in the axial than in the equatorial conformation. An equatorial C-OSiR(3) bond with one or two equatorial neighbors has a restricted potential energy well that becomes much broader when the bond is axial without any equatorial neighbors in the alternative chair. Adjacent silyl groups in the 1,2-disubstituted series interact in a stabilizing way overall in all conformations, this being particularly marked in the diaxial conformation of the more complex ethers. These factors lead to unusually large axial populations.  相似文献   

18.
Geometries and harmonic vibrational wave numbers were calculated on a series of simple compounds that contain the atoms of elements in the groups 14-17 by density functional theory at the B3LYP/6-311++G(3df,2pd) level. The calculated wave numbers agree well with the observed harmonic wave numbers with substantially the same accuracy for the compounds of the different groups. The stretching force constants of the CX (X = C, Si, Ge, N, P, As, O, S, Se, F, Cl and Br) single and multiple bonds were obtained. The CX stretching force constants increase with a decrease of the bond lengths as the element X in the same period goes from left to right in the periodic table. The individual intrinsic properties of the CX bonds are lost gradually with increasing the period of the element X. The unified interpretation of Badger's rule has enabled the formulation of a common equation for universal use f = 2.8 R(-3) to relate the force constants f (10(2) N m(-1)) and the reduced bond lengths R (10(-10) m).  相似文献   

19.
Cyclohexane (1), oxygen-, sulfur-, and/or nitrogen-containing six-membered heterocycles 2-5, cyclohexanone (6), and cyclohexanone derivatives 7-16 were studied theoretically [B3LYP/6-31G(d,p) and PP/IGLO-III//B3LYP/6-31G(d,p) methods] to determine the structural (in particular C-H bond distances) and spectroscopic (specifically, one bond (1)J(C-H) NMR coupling constants) consequences of stereoelectronic hyperconjugative effects. The results confirm the importance of n(X) --> sigma*(C-H)(app) (where X = O, N), sigma(C-H)(ax) --> pi*(C=O), sigma(S-C) --> sigma*(C-H)(app), sigma(C-S)-->sigma*(C-H)(app), beta-n(O) --> sigma*(C-H), and sigma(C-H) --> sigma*(C-H)(app) hyperconjugation, as advanced in previous theoretical models. Calculated r(C-H) bond lengths and (1)J(C-H) coupling constants for C-H bonds participating in more than one hyperconjugative interaction show additivity of the effects.  相似文献   

20.
The complex Tp(Ph,Me)NiS(2)CNMe(2) [Tp(Ph,Me) = hydrotris(3-phenyl-5-methyl-1-pyrazolyl)borate] features a bioinspired N(3)S(2) ligand set supporting a five-coordinate, trigonally distorted square-pyramidal geometry in the solid state. Spin crossover of Ni(II) was demonstrated by temperature-dependent X-ray crystallography and magnetic susceptibility measurements. The crystal lattice contains two independent molecules (i.e., Ni1 and Ni2). At 293 K, the observed bond lengths and susceptibility are consistent with high-spin (S = 1) Ni(II), and both molecules exhibit relatively short axial Ni-N bonds and long Ni-N and Ni-S equatorial bonds. At 123 K, the Ni1 complex remains high-spin, but the Ni2 molecule substantially crosses to a structurally distinct diamagnetic (S = 0) state with significant elongation of the axial Ni-N bond and offsetting contraction of the equatorial bonds. The temperature-dependent susceptibility data were fit to a spin equilibrium at Ni2 [ΔH° = 1.13(2) kcal/mol and ΔS° = +7.3(1) cal mol(-1) K(-1)] consistent with weak coupling to lattice effects. Cooling below 100 K results in crossover of the Ni1 complex.  相似文献   

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