Home Preparation and conformation of 3,4-anhydro-1,2-O-isopropylidene-5-O-mesyl-β-d-tagatopyranose and methyl 4-chloro-4-deoxy-1,3,5-tri-O-mesyl-β-d-fructopyranoside
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Preparation and conformation of 3,4-anhydro-1,2-O-isopropylidene-5-O-mesyl-β-d-tagatopyranose and methyl 4-chloro-4-deoxy-1,3,5-tri-O-mesyl-β-d-fructopyranoside

  • Jürgen Voss EMAIL logo , Kerstin Polchow-Stein and Gunadi Adiwidjaja
Published/Copyright: May 20, 2016
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 71 Issue 7

Abstract

The treatment of 3-O-acetyl-1,2-O-isopropylidene-4,5-di-O-methanesulfonyl-β-d-fructopyranose with sodium methoxide led to the crystalline epoxy-sugar 3,4-anhydro-1,2-O-isopropylidene-5-O-methanesulfonyl-β-d-tagatopyranose, the structure of which was determined by X-ray diffraction. Solvolysis of the epoxide with methanolic hydrogen chloride and subsequent mesylation gave methyl 4-chloro-4-deoxy-1,3,5-tri-O-methanesulfonyl-β-d-fructopyranoside which was also characterized by X-ray structure determination.

Keywords: chloro-sugar; epoxy-sugar; fructopyranoside; tagatopyranoside; X-ray structure determination

1 Introduction

In a comprehensive study, Buchanan and co-workers [1] have shown that the primary product of the treatment of 3,5-di-O-acetyl-1,2-O-isopropylidene-4-O-p-toluenesulfonyl-β-d-fructopyranose with sodium methoxide exhibits the 4,5-anhydro structure 1 rather than the expected isomeric 3,4-anhydro structure 2, which Ohle and Schultz had claimed for this compound in a publication of 1938 [2]. The structure of the crystalline 1 was proven by its characteristic 1H and 13C NMR spectra and definitely by an X-ray structure analysis [1]. This result is due to the known “epoxide migration” of oxiranes bearing a free vicinal hydroxy group [3]. However, in fact, a 2:1 equilibrium between 1 and 2 exists in the presence of methoxide and, consequently, also Ohle and Schultz’s oily isomer 2 can be isolated from this mixture by column chromatography.

During our investigations on anhydrothio-aldoses [4] and -ketoses [5] we came across a crystalline epoxide 5, which is closely related to 2 but, due to substitution of the necessary free hydroxy group, is unable to undergo the epoxide migration [5, 6]. In the following, the preparation, structural elucidation and follow-up reactions of 5 are described.

2 Results and discussion

Starting from d-fructose, we prepared 3-O-acetyl-1,2-O-isopropylidene-β-d-fructopyranose (3) [2, 7] via acetylation of 1,2:4,5-di-O-isopropylidene-β-d-fructopyranose [8, 9] and selective partial hydrolysis of the resulting 3-O-acetyl-1,2:4,5-di-O-isopropylidene-β-d-fructopyranose with dilute methanolic hydrogen chloride instead of sulfuric acid in n-propanol [2] or 80% aqueous acetic acid [7].

Mesylation of 3 in pyridine gave 3-O-acetyl-1,2-O-isopropylidene-4,5-di-O-methanesulfonyl-β-d-fructopyranose (4) with 96% yield. The treatment of the dimesylate 4 with sodium methoxide in methanol/dichloromethane at 5°C led to the epoxide 3,4-anhydro-1,2-O-isopropylidene-5-O-methanesulfonyl-β-d-tagatopyranose (5) in 85% yield (Scheme 1).

Scheme 1: (a) MeSO2Cl/pyridine; (b) NaOMe/MeOH/CH2Cl2, 0–5°C.
Scheme 1:

(a) MeSO2Cl/pyridine; (b) NaOMe/MeOH/CH2Cl2, 0–5°C.

The tagato-configuration of 5 was deduced from its NMR spectra. In particular, the proton signals of 3-H and 4-H at δ = 3.48 and 3.54 ppm, respectively, are shielded relative to 5-H and 6-H as expected for epoxide protons, and the corresponding coupling constant 3JH3,H4 = 3.5 Hz is characteristic of their di-equatorial position (cf. [1]). Also, the 13C NMR signals of C-3 and C-4 at δ = 50.53 and 55.54 ppm are shielded as compared to the signals of C-5 and C-6, which is typical for epoxy carbon atoms. The structure and configuration of 5 was finally confirmed by an X-ray structure determination. Figure 1 shows an Ortep plot of 5. The figure, as well as the characteristic torsion angles compiled in Table 1, clearly demonstrates the half-chair conformation (2HO) of the pyranose ring which has been observed also for 4,5-anhydro-1,2-O-isopropylidene-β-d-fructopyranose 1 (cf. Table 1 for comparison) [1].

Fig. 1: Ortep plot of 3,4-anhydro-1,2-O-isopropylidene-5-O-methanesulfonyl-β-d-tagatopyranose (5). Displacement ellipsoids are drawn at the 25% probability level, H atoms as spheres with arbitrary radii.
Fig. 1:

Ortep plot of 3,4-anhydro-1,2-O-isopropylidene-5-O-methanesulfonyl-β-d-tagatopyranose (5). Displacement ellipsoids are drawn at the 25% probability level, H atoms as spheres with arbitrary radii.

Table 1:

Selected dihedral angles (deg) of 5, 7, and, for comparison, of 1 [1].

C2–C3–C4–C5–4.758.818.3
C3–C4–C5–C6–18.5–55.5–3.5
C4–C5–C6–O652.654.318.0
C5–C6–O6–C2–67.6–58.3–51.2
C6–O6–C2–C342.159.467.8
O6–C2–C3–C4–5.9–59.5–47.5

Solvolysis of the epoxide 5 with hydrogen chloride in methanol under carefully controlled conditions selectively led to the methyl 4-chloro-4-deoxy-β-d-fructopyranoside 6 with inversion at C-4 according to the SN2-type intramolecular ring opening of the epoxide ring (Scheme 2).

Scheme 2: (a) HCl/MeOH; (b) MeSO2Cl/pyridine.
Scheme 2:

(a) HCl/MeOH; (b) MeSO2Cl/pyridine.

The chair conformation of the chloro-sugar 6 is evident from the typical trans-diaxial coupling 3JH3,H4 = 10.9 Hz between 3-H (δ = 3.83 ppm) and 4-H, the signal of which is low-field shifted to δ = 4.38 ppm due to the chloro substituent.

Mesylation of 6 yielded the trimesylate 7 as a crystalline solid. The structure, the-β-d-fructo-configuration and the expected chair conformation (1C4) of 7 were confirmed by its NMR spectrum (3JH3,H4 = 10.8 Hz) and corroborated by the X-ray structure analysis of a suitable single crystal; see Fig. 2 and the characteristic torsion angles of ca. ±60° in Table 1.

Fig. 2: Ortep plot of methyl 4-chloro-4-deoxy-1,3,5-tri-O-methanesulfonyl-β-d-fructopyranoside (7). Displacement ellipsoids are drawn at the 25% probability level, H atoms as spheres with arbitrary radii.
Fig. 2:

Ortep plot of methyl 4-chloro-4-deoxy-1,3,5-tri-O-methanesulfonyl-β-d-fructopyranoside (7). Displacement ellipsoids are drawn at the 25% probability level, H atoms as spheres with arbitrary radii.

Attempts to use 6 or 7 as starting materials for the preparation of thietano-sugars failed [10]. Application of the thio-Mitsunobu reaction, which represents a method of choice for the introduction of thioester functions into monosaccharides [4–6, 11], led to complete decomposition of 6 even under mild reaction conditions (room temperature). Also, the reaction of the trimesylate 7 with potassium thioacetate in dry DMF at 120°C did not yield any sugar thioacetate that could have been used for a ring closure reaction.

3 Experimental section

3.1 General

Melting points were determined by use of an electrothermal apparatus. Optical rotations were determined on a Perkin Elmer 341 polarimeter at λ = 589 nm in a 10-cm quartz cuvette. Thin layer chromatography (TLC) was performed on silica-coated aluminum foils (Merck, Darmstadt, Germany). The spots were visualized by UV light or by spraying with 20% H2SO4 in EtOH. Column chromatography (CC) was performed on silica gel 60 F (0.063–0.200 mm, Merck, Darmstadt, Germany). IR spectra (KBr pellets) were recorded on a Genesis Series FT-IR spectrometer (Mattson Instruments) and evaluated by use of the WinFirst 1.5 software (Analytical Technology Inc.). AMX 400 and DRX 500 NMR spectrometers (Bruker, Germany) were used. The spectra were recorded in CDCl3/SiMe4 or other suitable deuterated solvents. To improve the resolution of the spectra, they were recalculated from the respective free induction decays with the WinNMR 5.1 program (Bruker, Germany). Assignment of the signals was achieved with 1H–1H and 1H–13C correlation spectroscopy, distortionless enhancement by polarization transfer 135, and pendant experiments.

3.2 Preparations

3.2.1 3-O-Acetyl-1,2-O-isopropylidene-β-d-fructopyranose (3) [12]

A solution of 3-O-acetyl-1,2:4,5-di-O-isopropylidene-β-d-fructopyranose [7, 9] (2.0 g, 6.6 mmol) in MeOH (100 mL) was added to 0.1% HCl in MeOH (50 mL). The reaction mixture was stirred at room temperature for 14 h and then neutralized with NEt3 (three 0.9 mL portions). The solvents were removed (rotatory evaporator) and the residue was purified by CC (AcOEt) to yield 1.42 g (82%) of 3. – IR: ν = 2985, 2935, 2908, 2883, 1736 (C=O), 1376, 1319, 1244, 1184, 1088, 1072, 1063, 970, 903, 885, 874, 775, 731, 648, 594, 526, 503, 463 cm–1. – 1H NMR [12] (400 MHz, D2O, 20 mg): δ = 1.30 (s, 3H, CH3), 1.38 (s, 3H, CH3), 2.06 (s, 3H, COCH3), 3.64 (dd, 1H, 2JH6,H6′ = 12.9 Hz, 3JH5,H6 = 2.0 Hz, 6-H), 3.78 (d, 1H, 2JH1,H1′ = 9.8 Hz, 1-H), 3.84 (dd, 1H, 3JH4,H5 = 3.4 Hz, 3JH3,H4 = 10.2 Hz, 4-H), 3.87 (dd, 1H, 2JH6,H6′ = 13.0 Hz, 3JH5,H6′ = 1.9 Hz, 6′-H), 3.88 (d, 1H, 2JH1,H1′ = 9.7 Hz, 1′-H), 3.93 (dd, 1H, 3JH4,H5 = 3.3 Hz, 3JH5,H6′ = 1.6 Hz, 5-H), 5.37 (d, 1H, 3JH3,H4 = 10.2 Hz, 3-H) ppm. – 13C NMR [12] (100 MHz, D2O): δ = 20.73 (COCH3), 25.18 (CH3), 26.33 (CH3), 64.80 (C-6), 69.05 (C-4), 69.14 (C-3), 69.22 (C-5), 71.23 (C-1), 104.57 (C-2), 113.22 (CMe2), 173.68 (C=O) ppm.

3.2.2 3-O-Acetyl-1,2-O-isopropylidene-4,5-di-O-methanesulfonyl-β-d-fructopyranose (4)

The acetate 3 (1.17 g, 4.46 mmol) was dissolved in dry pyridine (11 mL). Under cooling with ice, methanesulfonyl chloride (1.4 mL, 18.0 mmol) was added to the solution. After 20 h stirring at room temperature, the solvent was removed (rotatory evaporator) and the residue was purified by CC (AcOEt–petroleum ether 3:1) to yield 1.78 g (96%) of crystalline 4; m.p. 142–143°C. – [α]D20 = -124.2 (c = 1.04, acetone). – IR: ν = 3037, 3020, 2995, 2939, 2885, 1745 (C=O), 1456, 1360 (SO2OR), 1292, 1244, 1178 (SO2OR), 1134, 1093, 1076, 1016, 991, 974, 962, 908, 881, 849, 822, 777, 762, 675, 636, 606, 536, 525, 507, 494, 463, 440 cm–1. – 1H NMR (400 MHz, [D6]acetone, 40 mg): δ = 1.40 (d, 3H, 5JH(Me),H1 = 0.4 Hz, CH3), 1.44 (d, 3H, 5JH(Me),H1 = 0.4 Hz, CH3), 2.12 (s, 3H, COCH3), 3.24 (s, 3H, SO2CH3), 3.25 (s, 3H, SO2CH3), 3.91 (d, 1H, 2JH1,H1′ = 9.4 Hz, 1-H), 3.96 (d, 1H, 2JH1,H1′ = 9.4 Hz, 1′-H), 4.02 (dd, 1H, 3JH5,H6 = 2.0 Hz, 2JH6,H6′ = 13.6 Hz, 6-H), 4.21 (dd, 1H, 3JH5,H6′ = 1.0 Hz, 2JH6,H6′ = 13.6 Hz, 6′-H), 5.08 (dd, 1H, 3JH4,H5 = 3.4 Hz, 3JH3,H4 = 10.4 Hz, 4-H), 5.24 (dd, 1H, 3JH4,H5 = 3.5 Hz, 3JH5,H6 = 2.0 Hz, 5-H), 5.25 (d, 1H, 3JH3,H4 = 10.4 Hz, 3-H) ppm. – 13C NMR (100 MHz, [D6]acetone, 40 mg): δ = 20.72 [C(O)CH3], 26.11 (CH3), 26.65 (CH3), 38.64 (SO2CH3), 38.82 (SO2CH3), 63.45 (C-6), 66.79 (C-3), 72.16 (C-1), 75.34 (C-4), 78.31 (C-5), 105.33 (C-2), 113.19 (CMe2), 170.64 (C=O) ppm.

3.2.3 3,4-Anhydro-1,2-O-isopropylidene-5-O-methanesulfonyl-β-d-tagatopyranose (5)

A solution of 4 (5.76 g, 13.77 mmol) in CH2Cl2 (100 mL) was added at 0°C to a solution of Na (1.61 g, 70.0 mmol) in MeOH (22 mL). The reaction mixture was kept at 5°C (refrigerator) for 4 days. The solution was washed with water. The organic layer was dried over MgSO4 and the solvent was removed (rotatory evaporator) to yield 3.26 g (85%) of pure (TLC), colorless crystals of 5; m.p. 122–123°C (decomposition). – [α]D20 = –29.0 (c = 1.0, CHCl3). – IR: ν = 3032, 3018, 3003, 2989, 2902, 1471, 1442, 1387, 1375, 1356 (SO2OR), 1271, 1234, 1211, 1174 (SO2OR), 1146, 1092, 1068, 1043, 985, 953, 895, 870, 849, 816, 793, 731, 692, 550, 509 cm–1. – 1H NMR (400 MHz, [D6]acetone, 40 mg): δ = 1.39 (s, 3H, CH3), 1.40 (s, 3H, CH3), 3.24 (s, 3H, SO2CH3), 3.48 (d, 1H, 3JH3,H4 = 3.5 Hz, 3-H), 3.54 (m, 1H, 4-H), 3.77 (dd, 1H, 2JH6,H6′ = 13.4 Hz, 3JH5,H6 = 0.8, 6-H), 3.96 (dd, 1H, 2JH6,H6′ = 13.4 Hz, 3JH5,H6′ = 1.7 Hz, 6′-H), 4.00 (d, 1H, 2JH1,H1′ = 9.2 Hz, 1-H), 4.18 (d, 1H, 2JH1,H1′ = 9.2 Hz, 1′-H), 4.97 (ddd, 1H, 3JH5,H6 = 0.4 Hz, 3JH5,H6′ = 1.7 Hz, 3JH4,H5 = 3.6 Hz, 5-H) ppm. – 13C NMR (100 MHz, [D6]acetone): δ = 26.28 (CH3), 26.97 (CH3), 38.15 (SO2CH3), 50.53 (C-4), 55.54 (C-3), 60.91 (C-6), 73.21 (C-5), 74.42 (C-1), 101.21 (C-2), 111.79 (CMe2) ppm.

3.2.4 Methyl 4-chloro-4-deoxy-5-O-methanesulfonyl- β-d-fructopyranoside (6)

The oxirane 5 (1.50 g, 5.53 mmol) was dissolved in a methanolic solution of 11.4% HCl, prepared from AcCl in MeOH (132 mL), and stirred at room temperature for 24 h. The solvent was removed (rotatory evaporator) and the residue washed with a little MeOH to yield 0.84 g (54%) of pure (TLC) 6 as a colorless solid. – IR: ν = 3527(OH), 3327, 3026, 3001, 2925, 2887, 2843, 1458, 1390, 1344 (SO2OR), 1281, 1265, 1174 (SO2OR), 1163, 1136, 1074, 1059, 1045, 1020, 999, 947, 920, 847, 818, 783, 692, 642, 594, 515 cm–1. – 1H NMR (500 MHz, [D6]DMSO): δ = 3.20 (s, 3H, OCH3), 3.24 (s, 3H, SO2CH3), 3.57 (d, 1H, 2JH1,H1′ = 11.5 Hz, 1-H), 3.60 (d, 1H, 2JH1,H1′ = 11.5 Hz, 1′-H), 3.75 (dd, 1H, 2JH6,H6′ = 13.2 Hz, 3JH5,H6 = 0.7 Hz, H-6), 3.83 (dd, 1H, 3JH3,OH = 8.1 Hz, 3JH3,H4 = 10.9 Hz, 3-H), 3.86 (dd, 1H, 2JH6,H6′ = 13.3 Hz, 3JH5,H6′ = 1.8 Hz, 6′-H), 4.38 (dd, 1H, 3JH3,H4 = 10.9 Hz, 3JH4,H5 = 3.2 Hz, 4-H), 4.86 (dd, 1H, 3JH1,OH = 6.6 Hz, 3JH1′,OH = 5.9 Hz, 1-OH), 5.01 (dd, 1H, 3JH5,H6′ = 1.5 Hz, 3JH4,H5 = 3.0 Hz, 5-H), 5.32 (d, 1H, 3JH3,OH = 8.1 Hz, 3-OH) ppm. – 13C NMR (100 MHz, [D6]DMSO): δ = 38.41 (SO2CH3), 48.74 (OCH3), 60.56 (C-4), 61.01 (C-1), 62.20 (C-6), 68.22 (C-3), 80.17 (C-5), 101.50 (C-2) ppm.

3.2.5 Methyl 4-chloro-4-deoxy-1,3,5-tri-O-methanesulfonyl-β-d-fructopyranoside (7)

The mesylate 6 (0.84 g, 2.89 mmol) and methanesulfonyl chloride (2.3 mL, 29.5 mmol) were reacted for 5 days in pyridine (14 mL) as described for the preparation of 4. CC (AcOEt) yielded 0.89 g (69%) of pure (TLC), colorless crystals of 7; m.p. 172–173°C. [α]D20 = -77.0 (c = 1.01, acetone). IR: ν = 3450, 3032, 3008, 2985, 2949, 2850, 1462, 1365 (SO2CH3), 1334, 1288, 1275, 1261, 1178 (SO2CH3), 1136, 1080, 1063, 1026, 1009, 966, 881, 849, 816, 673, 640, 609, 580, 548, 530, 517 cm–1. – 1H NMR (400 MHz, [D6]acetone): δ = 3.17 (s, 3H, SO2CH3), 3.26 (s, 3H, SO2CH3), 3.29 (s, 3H, SO2CH3), 3.41 (s, 3H, OCH3), 4.04 (dd, 1H, 2JH6,H6′ = 13.4 Hz, 3JH5,H6 = 1.1 Hz, 6-H), 4.13 (dd, 1H, 2JH6,H6′ = 13.4 Hz, 3JH5,H6′ = 1.9 Hz, 6′-H), 4.32 (d, 1H, 2JH1,H1′ = 11.1 Hz, 1-H), 4.55 (d, 1H, 2JH1,H1′ = 11.1 Hz, 1′-H), 4.79 (dd, 1H, 3JH3,H4 = 10.8 Hz, 3JH4,H5 = 3.1 Hz, 4-H), 5.01 (d, 1H, 3JH3,H4 = 10.8 Hz, 3-H), 5.24 (m, 1H, 5-H) ppm. – 13C NMR (100 MHz, [D6]acetone): δ = 37.68 (SO2CH3), 38.46 (SO2CH3), 39.05 (SO2CH3), 49.77 (OCH3), 57.43 (C-4), 63.25 (C-6), 67.74 (C-1), 76.61 (C-3), 79.73 (C-5), 99.24 (C-2) ppm.

3.3 X-ray structure determinations

The crystal data of 5 and 7 and a summary of experimental details are given in Table 2. The structures were solved by Direct Methods by use of the program Sir97 [13, 14], and refined by full-matrix least squares on F2 using all data (Shelxl-97 [15, 16]). Molecule plots: Ortep [17]. Crystallographic data of 3 and 5 have been deposited.

Table 2:

Crystal structure data for 5 and 7.

57
FormulaC10H16O7SC10H19ClO11S3
Mr280.29446.88
Crystal size (mm3)0.38 × 0.35 × 0.270.37 × 0.35 × 0.33
Crystal systemMonoclinicOrthorhombic
Space groupP21P212121
a (Å)5.519(1)8.634(1)
b (Å)10.289(1)14.913(1)
c (Å)11.453(1)15.025(1)
β (deg)96.61(1)90.00
V (Å3)646.00(14)1934.6(3)
Z24
Dcalcd (g cm–3)1.4411.534
μ(MoKα) (cm–1)0.2740.570
F(000) (e)296928
hkl range+7, +13, ±14+11, +19, +19
θmax (deg)27.4727.48
Reflections measured862021 786
Reflections unique15592529
Rint0.0360.043
Parameters refined192255
R(F)/wR(F2) (all data)a0.0517/0.13140.0503/0.1051
x(Flack)0.26(14)0.25(10)
GoF (F2)a1.1231.094
Δρfin (max/min) (eÅ–3)0.48/-0.250.34/-0.32

aRefinement on F2 for all reflections. The weighted R factor wR and goodness of fit GoF are based on F2; conventional R factors R are based on F, with F set to zero for negative F.

CCDC 182765 (5) and 182766 (7) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Acknowledgments:

We thank the University of Hamburg and the Fonds der Chemischen Industrie for financial support. K. P.-S. thanks the University of Hamburg for a Graduation Fellowship. U. Behrens, University of Hamburg, is acknowledged for his advice concerning the X-ray structure determinations.

References

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Received: 2015-12-3
Accepted: 2016-2-17
Published Online: 2016-5-20
Published in Print: 2016-7-1

©2016 by De Gruyter

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  9. Chromium(III) complexes with 1,2,4-diazaphospholide and 2,6-bis(N-1,2,4-diazaphosphol-1-yl) pyridine ligands: synthesis, X-ray structural characterization, EPR spectroscopy analysis, and magnetic susceptibility studies
  10. Synthesis and antimicrobial activity of some linear dipeptide pyridine and macrocyclic pentaazapyridine candidates
  11. Studies on the synthesis and properties of 1,1,1-trinitroprop-2-yl urea, carbamate and nitrocarbamate
  12. Gold nanocrystal arrays as electrocatalysts for the oxidation of methanol and ethanol
  13. Syntheses, single-crystal structures, vibrational spectra and DSC/TG analyses of orthorhombic and trigonal Ag[N(CN)2]
https://doi.org/10.1515/znb-2015-0204
Keywords for this article
chloro-sugar; epoxy-sugar; fructopyranoside; tagatopyranoside; X-ray structure determination

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  1. Frontmatter
  2. In this Issue
  3. Review
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  5. Synthesis of novel pyrazole derivatives using organophosphorus, stibine, and arsine reagents and their antitumor activities
  6. A highly efficient CuI nanoparticles-catalyzed synthesis of tetrahydrochromenediones and dihydropyrano[c]chromenediones under grinding
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  8. Preparation and conformation of 3,4-anhydro-1,2-O-isopropylidene-5-O-mesyl-β-d-tagatopyranose and methyl 4-chloro-4-deoxy-1,3,5-tri-O-mesyl-β-d-fructopyranoside
  9. Chromium(III) complexes with 1,2,4-diazaphospholide and 2,6-bis(N-1,2,4-diazaphosphol-1-yl) pyridine ligands: synthesis, X-ray structural characterization, EPR spectroscopy analysis, and magnetic susceptibility studies
  10. Synthesis and antimicrobial activity of some linear dipeptide pyridine and macrocyclic pentaazapyridine candidates
  11. Studies on the synthesis and properties of 1,1,1-trinitroprop-2-yl urea, carbamate and nitrocarbamate
  12. Gold nanocrystal arrays as electrocatalysts for the oxidation of methanol and ethanol
  13. Syntheses, single-crystal structures, vibrational spectra and DSC/TG analyses of orthorhombic and trigonal Ag[N(CN)2]
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