Crystal structure and solid state computational (DFT/Hirshfeld surface) study for probing a new efficient and recyclable oxidation reagent, 1,2-ethandiylbis(triphenylphosphonium) peroxodisulfate dihydrate

Article abstract of DOI:10.1080/10426507.2016.1206106

A new, efficient and recyclable reagent, 1,2-Ethandiylbis(triphenylphosphonium) peroxodisulfate dihydrate, for the oxidation of benzylic alcohols has been synthesized and characterized by IR, NMR spectroscopy, and single crystal X-ray crystallography. Usi

Full text of DOI:10.1080/10426507.2016.1206106

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Crystal structure and solid state computational
(DFT/hirshfeld surface) study for probing a
new efficient and recyclable oxidation reagent,
1,2-ethandiylbis(triphenylphosphonium)
peroxodisulfate dihydrate
R. Salmasi, A. R. Salimi, M. Gholizadeh, A. Abolghasempour & Jered C.
Garrison
To cite this article: R. Salmasi, A. R. Salimi, M. Gholizadeh, A. Abolghasempour & Jered
C. Garrison (2016): Crystal structure and solid state computational (DFT/hirshfeld
surface) study for probing a new efficient and recyclable oxidation reagent, 1,2-
ethandiylbis(triphenylphosphonium) peroxodisulfate dihydrate, Phosphorus, Sulfur, and
Silicon and the Related Elements, DOI: 10.1080/10426507.2016.1206106
To link to this article: http://dx.doi.org/10.1080/10426507.2016.1206106
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Jun 2016.
Published online: 28 Jun 2016.
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CRYSTAL STRUCTURE AND SOLID STATE COMPUTATIONAL (DFT/HIRSHFELD
SURFACE) STUDY FOR PROBING A NEW EFFICIENT AND RECYCLABLE
OXIDATION REAGENT, 1,2-ETHANDIYLBIS(TRIPHENYLPHOSPHONIUM)
PEROXODISULFATE DIHYDRATE
R. Salmasi1, A. R. Salimi1, M. Gholizadeh1*, A. Abolghasempour 1, Jered C. Garrison2
1
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad
91775-1436, I.R. IRAN
2 Department of Pharmaceutical Sciences, University of Nebraska Medical Center, 985830. USA
Corresponding Author E-Mail: m_gholizadeh@um.ac.ir
Abstract
A
new, efficient and recyclable reagent, 1,2-Ethandiylbis(triphenylphosphonium)
peroxodisulfate dihydrate, for the oxidation of benzylic alcohols has been synthesized and
characterized by IR, NMR spectroscopy and single crystal X-ray crystallography. Using the title
compound, the results indicate that the oxidation reactions are rapid, take place under mild
reaction conditions, easily to work-up and high yielding. The Hirshfeld surface and associated
finger print plots were derived from the X-ray structure to visualize the significant non-classical
C-H···O/π interactions in the crystal packing. The geometry, vibrational spectroscopy and
electronic properties of the bis(triphenylphosphonium) dication have also been investigated by
various DFT computational methods.
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Keywords Triphenylphosphonium salt, X-ray crystal structure analysis, Oxidation reagent,
Hirshfeld surface analysis, DFT computation.
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INTRODUCTION
The peroxodisulfate ion has been shown to be a strong oxidizing agent for a variety of
organic compounds 1-8. Some reported successful applications of this oxidant are oxidative
13
decarboxylation of acids9, aromatic hydroxylation 10-12, oxidation of alkyl benzenes , oxidation
of carbon-nitrogen double bonds 14,15, alkenes16-18, amines19, alcohols 20-23. Although the standard
redox potential of peroxodisulfate ion is high (about 2.01 V in aqueous solution) peroxodisulfate
•
can be employed to generate SO4 radical anions, one of the most important and strong one-
electron oxidants in organic synthesis. Its ability to oxidize different alcohols to corresponding
carbonyl compounds has been under intensive investigation in recent years24-28
.
Unfortunately, many of the peroxodisulfate reagents mentioned in the literatures suffer
from at least one of the following disadvantages: cost of preparation, instability, hygroscopicity,
photosensivity, lack of selectivity and tedious work-up procedures with accompanying reagent
decomposition. As a result there is still a need for the development of stable and efficient
oxidants to synthesize carbonyl compounds from their corresponding benzylic alcohols under
mild reaction conditions.
Herein,
we
report
the
synthesis
and
application
of
1,2-
ethandiylbis(triphenylphosphonium) peroxodisulfate dihydrate (1), a mild, efficient, inexpensive,
convenient and selective oxidant for the conversion of benzylic alcohols to their corresponding
carbonyl compounds in non-aqueous medium. We have described the crystal structure of this
new compound and the intermolecular interactions between bis(triphenylphosphonium) cationic
and peroxodisulfate anionic moieties by Hirshfeld surface analysis. In addition, density
functional theory (DFT) calculations were used to perform a structural analysis of the
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triphenylphosphonium cation moiety. Theoretical results indicate good agreement between the
FT-IR and the computational data with respect to the vibrational modes of 1.
RESULTS AND DISCUSSION
Crystal structure description
The ORTEP view of title compound is shown in Fig. 1. The single crystal x-ray analysis
shows that the molecules crystallize in the monoclinic system having chiral P21 space group. The
2+
2
asymmetric unit of 1 was found to contain C38H34P2 .S2O8
salt as 1:1 ratio of
bis(triphenylphosphonium) cation and peroxodisulfate anion with two water molecules. The
cations lie in general positions and the phosphorus atoms exhibit a slightly distorted tetrahedral
geometry. The bond angles around the P atoms are in the range of 107.7(2)° to 110.4(3)° for P1
and 105.8(2)° to 111.3(2)°for P2. The torsion angles of P1-C19-C20-P2 for the dication is
154.4(3)°. The geometry of the dications (bond lengths and angles) are general and comparable
with our previously reported periodate salt.29
The arrangement of the phenyl rings in the PPh3 moieties diverge from planarity with
deviations of 0.061, 0.029 and 0.125 Å, correspondingly, for the phenyl rings containing C1, C7
and C13 atoms attached to P1 and 0.275, 0.222 and 0.231 Å, respectively, for the phenyl rings
containing C21, C27 and C33 atoms attached to P2. The difference between the deviations of
phosphorus bond angles from ideal and phenyl rings from planarity are due to the PPh3
interactions. This issue will be further considered by Hirshfeld surface analysis in the next
section.
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In the crystal packing, the bis(triphenylphosphonium) dication and peroxodisulfate anion
are linked together by several CH···O hydrogen bonds with H···O distances ranging from 2.326
to 2.645 Å. The water molecules are involved in the hydrogen bond interactions with the anion
as a 1D chain along the a axis (Fig. 2). The cation moieties also interact through CH···π
interactions with each other with H···Cg (Cg is centroid of phenyl ring) distances ranging from
3.092 to 3.411 Å. As expected, the peroxodisulfate anion of 1 inserts into the 1D chain of
bis(triphenylphosphonium) dications in which each cation alternately links two anions along the
right-handed 1D helical chain (Fig. 3) Overall, the interactions result in a supramolecular
network of ionic moieties producing the three dimensional chiral pattern. The geometrical
parameters of hydrogen bonds are presented in Table 1.
Hirshfeld surface analysis
Main unit functionality of the [EDBTPP]2+ cation in the various crystalline environments
was considered based on the Hirshfeld surface analysis, which is an extremely useful method for
visualizing molecular contacts. The Hirshfeld surfaces were generated using Crystal Explorer 3.1
30
based upon the X-ray structure analysis. The red and blue colors in the Hirshfeld surface,
mapped with dnorm, are associated with distances that are shorter and longer than van der Waals
intermolecular contacts, respectively. The corresponding areas on the surfaces of cation and
anion moieties are shown as large circular depressions with red color. Indeed, these deep and
bright-red areas are due to the H∙∙∙O interactions with proportions of 20.8% for the cation and
94.2% for the anion. These significant interactions are represented as a sharp spike on the 2D
fingerprint plot (Fig. 4). The decomposition of the fingerprint plot shows that ‍C∙∙∙H contacts
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include 25.3% of total Hirshfeld surface area corresponded to the C-H∙∙∙π interactions which are
illustrated as characteristic wings at the top and bottom right sections of the plot.
To better understand the interactions of each PPh3 unit, the decomposed fingerprint plots
for close contacts were prepared. The proportions of CH∙∙∙O and CH∙∙∙π interactions are 28.3%
and 20.0% for phenyl rings of P1 and 27.7% and 15.9% for P2 atoms, respectively. It is clear that
the difference in the proportion of H···O atom pair contacts in the phenyl rings of P atoms
resulted in the different environment and consequently the slight different geometries of
phosphorous atoms.
Computational discussion
Structural characteristics of the [EDBTPP]2+ cation have been optimized at two levels of
theory (Fig. S 1 Supplemental Materials). The results of the B3LYP and B3PW91 geometry
optimizations for the bis(triphenylphosphonium) cation are presented in Table S1 in which bond
lengths and bond angles have been compared with those obtained experimentally. Overall, it can
be concluded that the DFT levels give comparable geometries, which differ from each other by
not more than 0.152 Å/0.154 Å in bond length and 4.66°/4.50° in bond angle, at the
B3LYP/B3PW91 levels, respectively.
Charge distributions on the [EDBTPP]2+ cation were calculated by the NBO method.
Natural charges on cation indicated that C atoms have negative character, while P and H atoms
have positive ones. Computed values of the natural charges for P, C and H have been reported in
Table S2. The energy gap between the highest occupied molecular orbital (HOMO) and the
lowest unoccupied molecular orbital (LUMO) in the cation is 128.6 kcal/mol. Figure S2 shows
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that the HOMO orbital is distributed around the phenyl rings, while the LUMO orbital is located
on the phosphorus atoms.
The molecular conformation obtained from the crystalline structure, as well as the one yielded by
geometry optimization, exhibits no special symmetries and hence the molecule belongs to the C1
point group. As a consequence, all of the 216 fundamental vibrations of the free molecule are
both IR and Raman active. Assigned wavenumbers of some of the selected vibrational modes
calculated at the B3LYP and B3PW91 levels, with experimental results, are presented in Table 2.
The highest frequency calculated at ca. 3175 cm−1 (B3LYP), was assigned to the asymmetric
stretching of CH in the aromatic rings. This frequency was observed as the weak intensity peak
experimentally at ca. 3056 cm−1. Moreover, the frequency of 3064 cm1 (B3LYP) with the
medium intensity was observed at ca. 2917 cm−1, assigned to symmetric stretching of C(sp3)-H.
The observed vibrations at ca. 1482 and 1589 cm−1 which were assigned to the symmetric
stretching of C-C bonds and bending of the H-C-C in the rings, calculated at ca. 1473 and 1623
cm−1, respectively. The other vibrations which were attributed to the bond stretching and bending
in the angle or wagging of the various bonds are described in Table 2.
Oxidation reagent activity
Herein, we wish to report that the title compound is a stable white solid oxidant reagent
able to perform oxidation of alcohols to their corresponding carbonyl compounds in acetonitrile
under reflux conditions. This catalyst is easily prepared from an aqueous solution of 1,2-
29
ethandiylbis(triphenylphosphonium) dibromide (C38H34Br2)
and potassium peroxodisulfate
solution at ambient temperature. This reagent is soluble in DMF, acetonitrile and negligible
soluble in dichloromethane and chloroform. The oxidant is not soluble in tetrahydrofuran, ethyl
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acetate and n-hexane. In order to find the optimum condition for the oxidation with 1, we have
chosen 4-chlorobenzyl alcohol as a model substrate. We have accomplished the oxidation in the
presence of different solvents such as DMF, dichloromethane, chloroform, acetonitrile, n-hexane
and also THF at room temperature and with different molar ratios of the oxidation agents in
acetonitrile solvent (Tables 3 and 4).
A variety of benzylic alcohols were oxidized to their corresponding carbonyl compounds
as shown in Table 5 (Entries 1-8). The benzyl alcohols with an electron donating group were
oxidized faster than substrates containing an electron withdrawing group (Entries 1-6, Table 5).
Furthermore, oxidation of benzhydrol to benzophenone was accomplished with excellent yields
(Entery7 Table5). Also, in the oxidation reactions investigated, the over-oxidation of products to
their corresponding carboxylic acids was not observed. The products were identified by
comparison of their physical and spectral data with those of authentic samples (melting point and
boiling point).35, 36
A noteworthy advantage of this reagent 1 lies in its ability to shorten the reaction time,
mildness of reaction conditions, ease of procedural work-up, stability and non-hygroscopicity of
the reagent and high yield of products.
CONCLUSION
In conclusion, we report the synthesis and characterization of the novel, easily prepared
and efficient oxidation agent 1,2-ethandiylbis(triphenylphosphonium) peroxodisulfate dihydrate
(1). The Hirshfeld surfaces analysis indicated that the CH···O and CH···π intermolecular
interactions play a crucial role in the stabilization of supramolecular assemblies. The detailed
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vibrational spectral analysis was performed by combining experimental and theoretical
information using various DFT levels of theory. In all oxidation reactions, one equivalent of the
oxidant reagent was consumed which shows the efficiency of the reagent and advantage of this
oxidant in comparison with other reported peroxodisulfate derivatives. The short reaction time,
mildness of reaction conditions, ease of procedural work-up, stability of the reagent, and high
yield of products are the other advantages of using this method.
EXPERIMENTAL AND METHODS
Materials and methods
Alcohols, 1,2-dibromoethane, triphenylphosphine, potassium peroxodisulfate were
purchased from Fluka and Merck Co and used without further purification. Solvents were
purified by standard methods. Infrared spectra (, cm1) were recorded as KBr disk on a
Shimadzu FT-IR 8440S spectrophotometer. 1H NMR and 13C NMR were carried out on a Bruker
AC, 300 MHz spectrometer (1H: 300 MHz, 13C: 75 MHz) with TMS as an internal reference and
DMSO-d6 and also CDCl3 as solvents. GCs were recorded by a Shimadzu 17a-GC
chromatograph. Elemental analysis was performed on a LECO 250 instrument. The reactions
were monitored by TLC using Silica gel plates. The products were identified by comparison of
their 1H NMR, 13C NMR, IR and GC spectra and physical data with those of authentic samples.
The Supplemental Materials contains sample characterization spectra and micrographs of I
(Figures S 3 – S 6)
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1,2-Ethandiylbis(triphenylphosphonium) peroxodisulfate dihydrate (C76H68S2O8)
(1). A solution of K2S2O8 (5 mmol, 1.35 g) in H2O (40 mL) was prepared in a 50 mL round
bottomed flask with a magnetic stirrer. 1,1′-(Ethane-1,2-diyl)-bis-(triphenylphosphonium)
dibromide (C38H34Br2)29 was added to this solution, and the reaction was stirred at ambient
temperature for 1h.The resulting white precipitate was filtered, washed with distilled water (2×10
mL) and dried in vacuum to yield 3.64 g 1 (98%). m.p.: 228-230°C. 1H NMR (DMSO):  = 4 (s,
CH2), 7.75, 7.95 (m, aromatic hydrogens) ppm. 13C NMR (DMSO):  = 135.9, 134.5, 130.8,
117.6, 15.9. IR: 689(s), 732(s), 1110(s), 1438(s), 1482-1589(m), 2917(w), 3056(w).
X-ray crystallography analysis
A single crystal suitable for X-ray diffraction analysis was obtained by slow evaporation
of a solution of 1 at room temperature. X-ray crystallographic data was collected at 100(2) K on
an Oxford Diffraction Excalibur PX Ultra diffractometer. The structure was solved by direct
methods31 and subsequent different Fourier maps and then refined on F2 by a full-matrix least-
square procedure using anisotropic displacement parameters. The structure was checked for
32
higher symmetry with the help of the program PLATON . For the title compound, the non-H
atoms were refined anisotropically and H-atoms were placed in the ideal positions. The structural
resolution procedure was performed using WinGX crystallographic software package.33
summary of crystallographic data and structural refinement is presented in Table 6.
A
CCDC 1474186 contains the supplementary crystallographic data for this paper. These
data can be obtained free of charge via www.ccdc.cam.ac.uk/retrieving.html or from the
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Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge, B2 1EZ, UK; fax +44
1223 336033; or deposit@ccdc.cam.ac.uk.
Computational details
The density functional theory (DFT) calculations were performed with the Gaussian 03
software.34 For the DFT calculation, a 6-311G (d, p) basis sets were placed, respectively, on all
atoms. All DFT geometry optimizations of investigated cation were carried out with B3LYP and
B3PW91 methods. All calculations employed direct SCF, for which the standard approach is
significantly faster and the maximum disk space required for integral storage for this system was
less than 1500 MB. Calculated vibrational frequencies were determined analytically at the fully
optimized geometry at the B3LYP/6-311G (d, p) and B3PW91/6-31G(d, p) levels of theory.
Natural bond orbital (NBO) analysis at the B3LYP/6-311G (d, p) level for all molecules gives
the natural electron population and the natural charge for each atom.
General procedure for oxidation of some benzylic alkohols with (1)
Benzyl alkohol (1 mmol) was dissolved in CH3CN (10 mL) in a 25 mL round bottomed
flask equipped with a condensor and a magnetic stirrer. Title oxidant (1 mmol, 1.30 g) was added
under reflux conditions. The progress of the reaction was monitored by TLC (eluent: n-
hexane/EtOAc 7:3). After completion of the reaction, the mixture was filtered and the solvent
was evaporated. The resulted crude product was purified on a silica-gel (20×20 cm) plate (n-
hexane/EtOAc 4:1). Pure carbonyl compounds were obtained in 87-98% yields, which were
characterized by comparison with authentic samples. (Scheme, Table 7)
Regeneration of ionic liquid
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Another
interesting
feature
of
this
method
is,
that
the
1,2-
ethandiylbis(triphenylphosphonium) cation could be recycled and reused for regeneration of the
reagent. On completion of the reaction, the residual solid materials were collected, dissolved in
DMSO, and treated with freshly prepared aqueous K2S2O8 to give 1 quantitatively.
ACKNOWLEDGMENT
The authors are grateful to the Ferdowsi University of Mashhad Research Council for the
financial support of the project Code Number 36987.
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REFERENCES
1. Rajkumar, G. A.; Murugesan, V. Synth. Commun.1999, 29, 2105-2114.
2. Alessandro, N.; Liberatore, L.; Tonucci, L.; Morvillo, A.; Bressan, M. J. Mol. Catal A 2001,
175, 83-90.
3. Shirini, F.; Mohammad poor-Baltork, I.; Hejazi, Z.; Heravi, P. Bull. Korean Chem. Soc.2003,
24, 517-518.
4. Shaabani, A.; Naderi, S.; Rahmati, A.; Badri, Z.; Darvishi, M.; Lee, D. G. Synthesis.2005,
3023-3025.
5. Hunsen, M. Tetrahedron Lett. 2005, 46, 1561-1564.
6. Anthony, P. A.; Yoonhyun, K. Tetrahedron Lett. 2005, 46, 5417-5419.
7. Huang, J. Y.; Li, S. J.; Wang, Y. G. Tetrahedron Lett. 2006, 47, 5637-5640.
8. Lei, M.; Hu, R. J.; Wang, Y. G. Tetrahedron Lett. 2006, 47, 3047-3050.
9. Anderson, J. M.; Kochi, J. K. J. Am. Chem. Soc.1970, 92, 1651-1659.
10. Walling, C.; Camaioni, D. M.; Kim, S. S. J. Am. Chem. Soc. 1978, 100, 4814-4818.
11. Walling, C.; Camaioni, D. M. J. Am. Chem. Soc. 1975, 97, 1603-1604.
12. Walling, C.; Johnson, R. A. J. Am. Chem. Soc. 1975, 97, 363-367.
13. Walling, C.; Zhao, C.; El-Taliawi, G. M. J. Org. Chem. 1983, 48, 4910-4914.
14. Mohammad poor-Baltork, I.; Hajipour, A. R.; Mohammadi, H. Bull. Chem. Soc. Jpn. 1998,
71, 1649-1653.
15. Mohammad poor-Baltork, I.; Hajipour, A. R.; Haddadi, R. J. J. Chem. Res. (S). 1999, 102-
103.
16. Permal, P. T. Synth. Commun. 1990, 20, 1353-1356.
13
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17. Citterio, A.; Arnoldi, C.; Minisci, F. J. Chem. Soc. Perkin Trans. 1983, 2, 531-533.
18. Fristad, W. E.; Peterson, J. R. Tetrahedron Lett. 1983, 24, 4547-4550.
19. Thomson, R. H.; Forrester, A. R.; Dewar, P. S. J. Chem. Soc. Perkin Trans. 1972, 1, 2862-
2865.
20. Walling, C.; Camaioni, D. M. J. Am. Chem. Soc. 1978, 100, 3267-3268.
21. Smook, M. E.; Hamilton, G. A. J. Am. Chem. Soc.1974, 96, 860-869.
22. Clerici, A.; Minisci, F.; Ogawa, K. Tetrahedron Lett. 1987, 19, 1149-1152.
23. Caronna, T.; Citterio, A.; Grossi, L.; Minisci, F.; Ogawa, K. Tetrahedron 1976, 32, 2741-
2745.
24. Hashemi, M. M.; Ahmadi Beni, Y. J. Chem. Res(S). 1999, 434-435.
25. Varma, R.; Meshran, H. M. Tetrahedron Lett. 1997, 38, 5427-5428.
26. Didier, B.; Philipe, C. Tetrahedron Lett. 1996, 43, 7725-7728.
27. Chen, F.; Wan, J.; Guam, C.; Yang, J.; Zhang, H. Synth. Commun. 1996, 26, 253-260.
28. Dave, P.; Byum, H. S.; Engel, R. Synth. Commun. 1986, 16, 1343-1346.
29. Gholizadeh, M.; Ebrahimpour, E.; Hojati, S. F.; Maleki, B. Arab. J. Chem. 2014, 7, 267-271.
30. Wolff, S. K.; Grimwood, D. J.; McKinnon, J. J.; Turner, M. J.; Jayatilaka, D.; Spackman, M.
A. University of Western Australia,2012.
31. Sheldrick, G.M.SHELX97: Program for Crystal Structure Solution and Refinement,
University of Göttingen, Göttingen, Germany, 1997.
32. Spek, A. L. Acta Crystallogr. 2009, 65, 148-155.
33. Farrugia, L .J. J. Appl. Crystallogr. 2012, 45, 849-854.
34. Frisch, M. J. et al. Gaussian 03, Revision A.7, Gaussian Inc., Pittsburgh, PA, 2003.
14
ACCEPTED MANUSCRIPT

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35. Aldrich Catalogue “Handbook of Fine Chemicals ", 2011, pp. 1-3216.
36. Nielsen, A. T.; Houlihan, W. J. Org. React. 1968, 16, 1-403.
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Table 1. Significant Intermolecular Interactions (interatomic distances in Å and bond angels in
°) found in the title structure.
D-H···A
D-H
0.852
0.866
0.864
0.930
0.930
0.930
0.930
0.930
-
H…A
2.213
1.862
2.030
2.520
2.610
2.645
2.326
2.457
-
D…A
D-H…A
159
169
165
149
143
127
170
130
-
O1W-H1W···O8
O1W-H2W···O3i
O2W-H4W···O1W
C6-H6···O3i
3.025(2)
2.737(5)
2.874(6)
3.348(6)
3.401(5)
3.294(6)
3.247(6)
3.136(6)
3.092
C11-H11…O6ii
C17-H17···O5
C18-H18···O1
C32-H32···O1W
C10-H10···Cg(1)iii
C14-H14···Cg(2)iv
C15-H15···Cg(1)iii
-
-
3.336
-
-
-
3.411
-
Symmetry codes: (i) -1+x, y, z, (ii) 1-x, ½+y , 1-z, (iii) 1-x, ½+y , 1-z (iv) -x, ½+y , 1-z, (iv) x,
½-y, -1/2+z, Cg(1) and Cg(2) are centroid of phenyl rings containing C21, C27 atoms,
respectively.
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Table 2. Some selected theoretical and experimental vibrational (IR) wavenumbers (in cm−1) of
the [EDBTPP]2+ cation.
Vibrational
mode
B3LYP/6-
311G(d,p)
B3PW91/6-
31G(d,p)
EXPa
IR
Assignment
IR
Intensity
IR
Intensity
3175
3175
3170
3064
1623
1623
1623
1622
1515
1514
1473
1472
1472
1469
1468
1362
1360
1236
1215
1153
1115
1114
1111
1110
1110
1012
763
4.36
7.75
6.67
14.32
18.7
17
3200
3199
3198
3083
1647
1647
1647
1647
1523
1521
1481
1479
1479
1476
1462
1379
1344
1225
1214
1145
1128
1126
1121
1120
1118
1008
764
5.6
4.5
8.2
17.36
16.9
8.8
13.2
9.46
11.1
9.9
58.8
40.3
4.4
54.1
17.97
4.2
휐190
휐189
휐187
휐184
휐182
휐179
휐178
휐177
휐170
휐168
휐163
휐162
휐161
휐160
휐158
휐155
휐151
휐142
휐137
휐129
휐127
휐126
휐122
휐121
휐120
휐100
휐74
휐as(C(sp2) –H)
휐as(C(sp2) –H)
휐as(C(sp2) –H)
3056 w
2949 w
2917 m
휐s(C(sp3) –H)
휐s(C(sp2) – C(sp2))+ δs(H-
휐s(C(sp2) – C(sp2))+ δs(H-
10
4.5
1589 m 휐s(C(sp2) – C(sp2))+ δs(H-
휐s(C(sp2) – C(sp2))+ δs(H-
휐s(C(sp2) – C(sp2))+ δs(H-
휐s(C(sp2) – C(sp2))+ δs(H-
1482 m 휐s(C(sp2) – C(sp2))+ δs(H-
휐s(C(sp2) – C(sp2))+ δs(H-
14.4
11.9
50.2
36.5
6.6
25.7
42.11
6.6
휐s(C(sp2) – C(sp2))+ δs(H-
1438 s
δas (H-C(sp3) -H)
1404 w δs (H-C(sp3) -H)+ δs(H-C-
δs(H-C-C Ring)
16.8
38.03
7.9
9.7
δs(H-C-C Ring)
20.5
45.6
102.9
14.1
124
34.8
5.2
23.3
13.9
27.4
137
175
103
1269 s
1220 w
1141 s
τs (CH2)
τs (CH2)+ δas(H-C-C
τas (CH2)
δs(H-C-C Ring)
δs(H-C-C Ring)
δs(H-C-C Ring)
δas(H-C-C Ring)+휐(P-
δs(H-C-C Ring)+휐(P-
58.9
16.7
13.2
106.2
16.8
18.9
24.2
54.05
142.4
89.6
161.7
1111 s
1044 s
1001 m δs(C-C-C Ring) as(Ring-
818m
732 s
τs (C1,2,3,4,5,6-H)
τ as (CH2)+ τs (C2,4,6-H)
δ(C-C-CRing)
748
733
727
750
742
734
휐71
휐70
휐69
휐as(P-CH2)+ δ(C-C-
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707.9
705
705
703.7
672
534.5
509
8.5
36.7
24.2
54.4
29.5
115
92.9
73.4
26.04
709.5
702.5
702
700
676
534.7
509
493
5.3
25
43
43.1
15
112.5
78.6
64
τ (C2,4,6-H)+ τ as (CH2)
τ (C2,4,6-H)
τ (C2,4,6-H)+ τ as (CH2)
τ (C2,4,6-H)
휐65
휐63
휐62
휐61
휐58
휐50
휐49
휐46
휐34
689 m
673 m
527 m
휐as(P-CH2)
δ(CH2-P-Ring)+τ(C-H)
τ (CH2)+τ(C1,3,5-H)
τ (C-H)+τ(P-CH2)
τ (C2,4,6-H)+τ(P-CH2)
492.7
365
365
26.4
a The IR indication (s, strong; m, medium; w, weak) of the relative intensity in the experimental
IR is given, b The assignment indications are 휐as:: asymmetric stretching; 휐s; symmetric
stretching; δ; bending; τ: wagging.
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Table 3. Optimizing oxidation condition of 4-chlorobenzyl alcohol using 1 in different solvents
Entries
Solvent
DMF
Amount of oxidizing 1
Reaction
Yield(%)a
1
2
3
4
5
1
1
1
1
1
Immediately
98
60
CH2Cl2
10
15
10
5
CH3COOCH2CH3
CHCl3
N.R.
10
CH3CN‍
98
a) Yields refer to isolated products.
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Table 4. Optimizing oxidation condition of 4-chlorobenzyl alcohol using different amount of 1
Yields refer to isolated products.
Amount Reaction Yield (%)
of
time(min.
)
oxidizing
1 (mmol)
1
2
3
4
1
0.75
0.5
5
5
10
10
98
94
90
44
0.25
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Table 5. Oxidation of various alcohols using title compound in acetonitrile under reflux
conditions
Yieldb (%)
Entries
1
Substrate
Producta
Mp or bp (°C) 35, 36
(Time)
98 (5min)
47-50
OH
O
Cl
Cl
Cl
Cl
Br
2
95 (10 min)
212-214
OH
O
Br
3
4
90 (5 min)
98 (5 min)
229-231
55-58
OH
O
OH
O
Br
Br
5
90 (25 min)
105-108
OH
O
O2N
O2N
NO2
NO2
6
7
87 (25 min)
95 (10 min)
42-44
47-51
OH
O
OH
O
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8
96 (5 min)
177-179
OH
O
a) Yields refer to isolated products. All products presented as 2,4-dinitrophenylhydrazones.
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Table 6. Structural data and refinement for title compound
Chemical formula
Mr
C38 H38O10P2S2
780.74
Crystal system, space group
Temperature (K)
a, b, c (Å)
Monoclinic, P21
100
9.2919(3), 19.9092(6), 9.7425(3)
β (˚)
90.398(3)
1802.26(10)
2
V (Å3)
Z
Radiation type
μ (mm-1)
CuKα
2.683
Crystal size (mm)
Diffractometer
Absorption correction
Tmin, Tmax
0.15 × 0.15 × 0.15
Xcalibur, Onyx, Ultra
Multi-scan
0.8320, 1.000
13141, 6855
1.059
No. of measured, unique
GOOF
R1(I>2σ(I))
0.0495
wR2(I>2σ(I))
0.1295
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Fig. 1. ORTEP diagram of the asymmetric unit of the title salt, with atom labels and 50%
probability displacement ellipsoids for non-H atoms. Hydrogen atoms are not shown for clarity.
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Fig. 2. Illustration of hydrogen bonds chain of peroxodisulfate anion and water molecules along
the a axis. The cations are omitted for clarity.
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Fig. 3. Representation of the helical chain of 1 along the b axis. For clarity, the 1D chains are
presented alternatively.
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Fig 4. Representation of the Hirshfeld surface (left) and finger print plot (right) of [EDBTPP]2+
cation (top) and peroxodisulfate anion (down).
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Scheme. The oxidation reaction of alcohols by recyclable title reagent
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