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Synthesis and characterization of GeH2Cp*2 and its structural comparison with SiXHCp*2(X=Cl, H) and SnCl2Cp*2

  • Ronny Fritzsche , Tobias Rüffer , Heinrich Lang and Michael Mehring EMAIL logo
Published/Copyright: April 29, 2017
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Main Group Metal Chemistry
From the journal Main Group Metal Chemistry Volume 40 Issue 1-2

Abstract

The organogermane GeH2Cp*2 (1) was synthesized by the reaction of GeCl2Cp*2 (A) with LiAlH4 in quantitative yield, whereas the synthesis of the previously reported compounds SiCl2Cp*2 (B), SnCl2Cp*2 (C), SiClHCp*2 (D) and SiH2Cp*2 (E) followed established routes. The molecular structures of the Cp*M(IV) derivatives 1, B, D and E are reported. In addition, compound 1 was characterized by spectroscopic methods such as 1H and 13C{1H} NMR spectroscopy, ATR-FTIR spectroscopy and EI-mass spectrometry. The thermal behavior of the germanes 1 and A was investigated by thermogravimetric analysis (TGA, DSC) and PXRD. The decomposition of compounds A and 1 starts at 270°C (A) and 200°C (1), respectively. The formation of crystalline Ge upon heating these compounds in sealed quartz glass capillaries was observed at 270°C (A) and 500°C (1).

Keywords: crystal structure; decomposition behavior; germanium; pentamethylcyclopentadienyl; silicon; tin

Introduction

The synthesis, characterization and functionalization of germanium-containing materials, which are, for example, suitable for energy transformation and storage, are currently investigated intensely (Wu et al., 2016). Molecular precursors are of interest as a result of their volatility and solubility, and examples such as GeH2Ph2, GeH2tBu2, GeI2 and GeH3Cp* were successfully employed to produce germanium nanowires (Lu et al., 2013; Mullane et al., 2013), nanoparticles (Zaitseva et al., 2007; Muthuswamy et al., 2013) and thin films (Dittmar et al., 2001; Dittmar, 2002), all of which hold great potential as anode materials for lithium ion batteries (Liang et al., 2013; Jin et al., 2014; Xiao and Cao, 2014; Xu et al., 2014; Sun et al., 2015). The germanes GeH2Cp2* (1) and GeCl2Cp2* (A) might serve as superior precursors as compared to the above mentioned examples, due to an expected combination of high volatility, low sensitivity towards air and moisture, long-term stability and low decomposition temperature. Synthesis protocols for GeCl2Cp2* (A) exist (Jutzi and Hielscher, 1985, 1986; Jutzi et al., 1986; Filippou et al., 2002), but GeH2Cp2* (1) was not reported so far. It is noteworthy that the syntheses for the lighter and the heavier homologues of A, SiCl2Cp2* (B) (Jutzi et al., 1986, 1988a,b, 1989; Evans et al., 1990) and SnCl2Cp2* (C) (Jutzi and Kohl, 1979; Jutzi et al., 1986; Naseri et al., 2010; Erickson et al., 2014), as well as for SiH2Cp2* (D) (Jutzi et al., 1988a,b; Dahlhaus et al., 1993) and SiHClCp2* (D) (Jutzi et al., 1988a,1988b, 1993) are well documented, but only for the dichlorosilane B was the molecular structure in the solid state reported (Jutzi et al., 1988a,b). Herein, the synthesis and characterization of the germane GeH2Cp2* (1) is described, its thermal stability is compared with GeCl2Cp2* (A) and its molecular structure is discussed with comparison to other derivatives within the family of compounds of the type MX2Cp2* (M=Si, Ge, Sn; X=H, Cl).

Results and discussion

The organogermane 1 was synthesized by a hydrogenation reaction starting from GeCl2Cp*2 (A) with LiAlH4 in quantitative yield. It is worthy to note that various attempts to synthesize the heavier homologue SnH2Cp*2 by hydrogenation of the stannane SnCl2Cp*2 (C) with LiAlH4 or diisobutylaluminum hydride (DIBAL-H) at either 20°C or −40°C failed, and an immediate reduction to elemental β-tin was always observed as indicated by powder X-ray diffraction (PXRD) analysis. The compounds of the type MX2Cp*2 (A, M=Ge, X=Cl; B, M=Si, X=Cl; C, M=Sn, X=Cl; D, M=Si, X=H/Cl; E, M=Si, X=H) were prepared according to literature methods (Jutzi and Kohl, 1979; Jutzi et al., 1986, 1988a,b).

The 1H NMR spectrum of 1 shows a singlet resonance corresponding to the GeH2 protons at 3.91 ppm, which is shifted significantly downfield compared to the SiH2 protons of SiH2Cp*2 (E) (3.49 ppm) (Jutzi et al., 1988a,b), and the GeH2 protons of other germanes, such as GeH2Me2 (3.72 ppm) (Erickson et al., 2014) or GeH2tBu2 (3.67 ppm) (Kraft et al., 2011). The attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectrum of 1 shows a strong band at 2008 cm−1 that is assigned to the Ge-H stretching vibration. Despite C2ν symmetry of 1, only the νsym(GeH2) vibration band is observed, which is in accordance with reports on other Cp substituted metal hydrides of C2ν symmetry such as MoH2Cp2 and WH2Cp2 (Girling et al., 1986; Belkova et al., 2012). This band is shifted to lower wavenumbers compared to its lighter homologue SiH2Cp*2 (E) (2111 cm−1). Similar to silane E, germane 1 is stable under inert conditions but decomposes slowly when it is exposed to air and moisture.

Single crystals of compounds 1 and C–E were grown by slow cooling of concentrated diethyl ether solutions containing the appropriate species to −30°C. The molecular structures of the germane 1, stannane C, and silanes D and E are shown in Figures 1–4 , and selected bond lengths (Å) and angles (°) are given in Table 1. The crystallographic parameters are summarized in Table 2.

Figure 1: ORTEP at 40% probability for the carbon and germanium atoms and atom numbering scheme for compound 1.Hydrogen atoms of the methyl groups are omitted for clarity. Hydrogen atoms at the germanium are given in ball and stick type.
Figure 1:

ORTEP at 40% probability for the carbon and germanium atoms and atom numbering scheme for compound 1.

Hydrogen atoms of the methyl groups are omitted for clarity. Hydrogen atoms at the germanium are given in ball and stick type.

Figure 2: ORTEP at 50% probability and atom numbering scheme for compound C.Hydrogen atoms of the methyl groups are omitted for clarity. Disorder of the chlorine atoms is not shown.
Figure 2:

ORTEP at 50% probability and atom numbering scheme for compound C.

Hydrogen atoms of the methyl groups are omitted for clarity. Disorder of the chlorine atoms is not shown.

Figure 3: ORTEP at 20% probability and atom numbering scheme for compound D.Hydrogen atom of the methyl groups are omitted for clarity. The hydrogen atom at the silicon is given in ball and stick type.
Figure 3:

ORTEP at 20% probability and atom numbering scheme for compound D.

Hydrogen atom of the methyl groups are omitted for clarity. The hydrogen atom at the silicon is given in ball and stick type.

Figure 4: ORTEP at 40% probability and atom numbering scheme for compound E.Hydrogen atoms of the methyl groups are omitted for clarity. Hydrogen atoms at the silicon are given in ball and stick type.
Figure 4:

ORTEP at 40% probability and atom numbering scheme for compound E.

Hydrogen atoms of the methyl groups are omitted for clarity. Hydrogen atoms at the silicon are given in ball and stick type.

Table 1:

Selected bond distances and angles of compounds 1 and A–E.

GeH2Cp*2 (1)GeCl2Cp*2 (A)SiCl2Cp*2 (B)SnCl2Cp*2 (C)SiHClCp*2 (D)SiH2Cp*2 (E)
5.43°5.90°5.40°−6.90°5.15°7.66°
19.097 (2)°15.1 (4)°18.5 (2)°19.182 (6)°19.419 (6)°18.892 (2)°
5.56°3.90°6.80 °8.70°4.77°5.60°
3.70 Å3.80 Å3.50 Å3.92 Å3.52 Å3.57 Å
M-C1.987 (4) Å1.977 (5) Å1.885 (3) Å2.199 (2) Å1.925 (15) Å1.909 (2) Å
∠C-M-C121.4 (3)°127.3 (2)°122.5 (1)°129.733 (3)°121.1 (7)°121.3 (2)°
∠R-M-R (R=H; Cl)123.632 (3)°98.98 (11)°101.08 (5)°91.862 (4)°110.246 (4)°104.327 (2)°
Table 2:

Crystallographic data of compounds 1, C, D and E.

CompoundGeH2Cp*2 (1)SnCl2Cp*2 (C)SiHClCp*2 (D)SiH2Cp*2 (E)
Empirical formulaGeC20H32SnCl2C20H30SiClC20H31SiC20H32
Formula weight (g/mol)345.04460.03334.99300.54
Temperature (K)105120180105
Wavelength (Å)1.541840.710731.541841.54184
Crystal systemOrthorhombicMonoclinicMonoclinicOrthorhombic
space groupFdd2P21CcFdd2
a (Å)29.8103 (16)8.6158 (10)8.6010 (18)29.609 (2)
b (Å)15.1892 (10)15.4099 (14)15.271 (2)15.2187 (8)
c (Å)8.4152 (6)8.8565 (10)15.7317 (2)8.3873 (6)
α (°)90909090
β (°)90116.660 (14)104.98 (2)90
γ (°)90909090
V (Å3)3810.4 (4)1050.9 (2)1996.1 (5)3779.5 (4)
Z8248
Density (calculated) (g/cm3)1.2031.4541.1151.056
Absorption coefficient (mm−1)2.1011.4682.2101.014
F(000)14724687281328
crystal size (mm3)0.4×0.3×0.20.4×0.4×0.140.16×0.16×0.140.24×0.22×0.12
θ range for data collection5.94 to 62.99°2.957 to 24.9875.82 to 62.87°5.98 to 62.71°
Limiting indices‒34≤h≤30

‒17≤k≤17

‒9≤l≤9		‒9≤h≤10

‒18≤k≤18

‒10≤l≤10		‒9≤h≤8

‒15≤k≤17

‒12≤l≤18		‒33≤h≤34

‒17≤k≤17

‒9≤l≤7
Reflections collected4464928731125055
Independent reflections1387 (Rint=0.0298)3663 (Rint=0.0925)1913 (Rint=0.0409)1270 (Rint=0.0247)
Completeness98.8%99.7%97.6%99.2%
Refinement methodFull-matrix least-squares on F2Full-matrix least-squares on F2Full-matrix least-squares on F2Full-matrix least-squares on F2
Data/restraints/parameters1387/3/1003663/228/1691913/2/2041270/2/100
Final R indices [I>2σ(I)]R1=0.0534

wR2=0.1387		R1=0.0950

wR2=0.2283		R1=0.1302

wR2=0.3325		R1=0.0433

wR2=0.1256
R indices (all data)R1=0.0542

wR2=0.1403		R1=0.1013

wR2=0.2329		R1=0.1463

wR2=0.3606		R1=0.0438

wR2=0.1268
Goodness of fit on F21.0951.1491.4131.067
Largest difference peak and hole (eÅ−3)1.095 and −0.3751.348 and −1.5550.747 and −0.4370.207 and −0.172

In all molecular structures of the type MX2Cp*2 the metal atom (Si, Ge or Sn) is σ-bonded to the Cp* ring, and the latter exhibits a diene-like structure indicated by C-C single bonds (1.47–1.51 Å) and C=C double bonds (1.33–1.34 Å). The main features of all molecules are coplanar orientated Cp* rings, which are slightly parallel displaced and not congruent. This was also observed in the case of compounds such as SCp*2 (Bard et al., 1985), BClCp*2 (Macdonald et al., 2008), PClCp*2 (Pietschnig et al., 1997) and (GaClCp*2)2 (Beachley et al., 1985). For germane 1 the Cp* planes exhibit a dihedral angle (Table 1) of 5.43°, a value which is significantly lower than that of the corresponding silane E showing a value of 7.66°, but it is placed in the range as found for compounds A–D (5.15–5.83°). By contrast, the stannane C exhibits an angle of −6.90°, thus indicating attractive dispersion type interactions between the Cp* ligands. Compound 1 shows a typical parallel displacement of the Cp* groups (Table 1) of 19.10°, which is significantly larger than that in germane B with a value of 15.08°. A view along the c axis shows that the C1-M-C1′ plane (M=Si, Ge, Sn) (Table 1) is not orthogonal to the Cp* ring plane and is tilted by 5.56° for germane 1 and thus falls in the typical range from 3.89° to 6.83° (Table 1). As expected, the distance between the two Cp* ring centroids of 3.70 Å for 1 and 3.76 Å for B is greater, when compared to those of the silanes (3.52 Å), and less than for the tin homologues (3.92 Å). Due to the steric demand of the two Cp* rings, the tetrahedral angles around the germanium atom in compound 1 are significantly distorted C(1)*-Ge(1)-C(1) 121.4 (3)°, and the Ge-C bond is slightly elongated to 1.987 (4) Å as compared to GeH2Mes2 (1.965 Å) (Samanamu et al., 2011). The change of the metal atoms (Si, Ge and Sn) in the compounds A–C shows increasing M-C bond distances from 1.885 (3) (B), 1.977 (5) (A) to 2.172 (19) (C), leading to a decrease of intermolecular interaction between the two Cp* rings, and is reflected by the reduced Cp* dihedral angle and more parallel displacement.

The thermal behavior of the germane 1 and A was investigated by means of thermogravimetric analysis measurements and by temperature-dependent PXRD, with respect to our current interest in germanium-containing hybrid materials and thin films (Fritzsche and Mehring, 2016; Kitschke et al., 2016a,b). Heating to 550°C yielded a residue of 8.5% for 1 and 3.4% of A only, demonstrating significant volatility. The decomposition products from the thermogravimetric experiments were analyzed by energy dispersive X-ray/scanning electron microscope measurements, showing that the residue of germane 1 consists of 89.3% germanium, 9.4% carbon and 1.3% oxygen and the residue of germane B consists of 80.3% germanium, 17.6% carbon, 1.7% oxygen and 0.4% chlorine.

Temperature-dependent PXRD studies of GeH2Cp*2 (1) measured in a sealed quartz glass capillary showed that reflections disappear at 85°C due to melting and crystalline germanium starts to form at around 550°C (Figure 5). The formation of germanium from GeCl2Cp*2 (B) occurs at significantly lower temperatures than for germane 1 (Figure 6). The temperature-dependent PXRD analysis of A shows a phase transition at 140°C and the formation of crystalline germanium at 270°C. In the case of germane 1 the formation of amorphous germanium is assumed followed by crystallization between 500 and 600°C. It is noteworthy that the crystallization temperature of germanium depends significantly on the annealing conditions and preparation methods (Chik and Lim, 1976; Morimoto et al., 1984). The crystallization of amorphous germanium even below 400°C is reported if metals acting as nucleation seeds like Al [180°C (Toko et al., 2014) or 325°C (Oya et al., 2014)], Sn [450°C (Mullane et al., 2013)], Cu or Ag [380°C (Lu et al., 2013)] are present. The reason for the low crystallization temperature of B might be the presence of carbon. It has been reported that a phase segregation process from metastable germanium carbon alloys results in the formation of germanium nanocrystals even at low temperatures (Morimoto et al., 1984; John et al., 1997).

Figure 5: Temperature-dependent PXRD of 1 in sealed quartz glass capillaries confirming the formation of Ge (ICDD No. 00-004-0545).
Figure 5:

Temperature-dependent PXRD of 1 in sealed quartz glass capillaries confirming the formation of Ge (ICDD No. 00-004-0545).

Figure 6: Temperature-dependent PXRD of A in sealed quartz glass capillaries, confirming the formation of Ge (ICDD No. 00-004-0545).
Figure 6:

Temperature-dependent PXRD of A in sealed quartz glass capillaries, confirming the formation of Ge (ICDD No. 00-004-0545).

Conclusion

The germane GeH2Cp*2 (1) was prepared in quantitative yield by hydrogenation of GeCl2Cp*2with LiAlH4. Data obtained by 1H and 13C{1H} NMR, ATR-FTIR spectroscopy and electron ionization (EI)-mass spectrometry (MS) are consistent with the formation of 1. The molecular structure of 1 exhibits σ-bonded Cp* rings that are orientated parallel towards each other, slightly parallel displaced and not congruent. Similar structures are observed for compounds of the type MX2Cp*2 (C, M=Sn, X=Cl; D, M=Si, X=H/Cl; E, M=Si, X=H). All compounds, despite SnCl2Cp*2 (C), show Cp* rings, that are tilted against each other. Thermal analysis is consistent with the formation of crystalline germanium upon decomposition. Thus, the volatile germane 1 might be used for deposition of germanium thin films at rather low temperature.

Experimental section

General procedure

All reactions were carried out under argon atmosphere using standard Schlenk techniques or in a glovebox under argon atmosphere. Diethyl ether, tetrahydrofuran, toluene and n-hexane were purified by distillation from sodium. CH3CN was dried prior to use by distillation from CaH2. All other chemicals were purchased from commercial suppliers. n-Butyl lithium (2.5 m in n-hexane, Acros Organics, Hampton, NH, USA), lithium aluminum hydride (97%, Alfa Aesar, Ward Hill, MA, USA), SiCl4 (99%, Alfa Aesar, Ward Hill, MA, USA), SiHCl3 (99%, Sigma-Aldrich, St. Louis, MO, USA), GeCl4 (99%, ABCR, Karlsruhe, Germany), SnCl4 (99%, Sigma-Aldrich, St. Louis, MO, USA) and DIBAL-H (97%, Sigma-Aldrich, St. Louis, MO, USA) were used as received. 1,2,3,4,5-Pentamethylcyclopentadiene (Cp*H) (Fendrick et al., 1992), A (Jutzi et al., 1986), B (Jutzi et al., 1988a,b), C (Jutzi et al., 1986), D (Jutzi et al., 1988a,b) and E (Jutzi et al., 1988a,b) were synthesized according to literature methods. The lithium salt of Cp* was synthesized according to modified literature procedures with n-butyllithium in tetrahydrofuran (Jutzi et al., 1988a,b).

ATR-FTIR spectra were measured with a BioRad FT-IR 165 spectrometer (Bio-Rad Laboratories, Philadelphia, PA, USA) with Golden Gate ATR (LOT-Oriel GmbH and Co. KG, Darmstadt, Germany). NMR spectra were recorded using a Bruker Avance III 500 (Bruker Corporation, Billerica, MA, USA) (500.3 MHz for 1H, 125.7 MHz for 13C{1H}). Chemical shifts (δ) are reported in parts per million (ppm) relative to tetramethylsilane (TMS) using the solvent as internal reference (CDCl3: 1H NMR δ 7.26 ppm). Microanalysis was performed by using a Thermo Fischer FlashAE 1112 (Thermo Fisher Scientific Inc., Waltham, MA, USA). The melting points (sealed off in argon flushed capillaries) were determined using a Büchi Melting Point B-540 (Büchi Labortechnik GmbH, Essen, Germany). EI-MS was performed with a Shimadzu GC-17A Gas Chromatograph and GC-MS-QP5000 Gas Chromatograph Mass Spectrometer (Shimadzu Corp, Kyōto, Japan). The PXRD patterns were collected using a STOE-STAD IP diffractometer from STOE (STOE and Cie GmbH, Darmstadt, Germany) with Cu-Kα radiation (40 kV, 40 mA) and a Ge (111) monochromator. All decomposition experiments were carried out in a nitrogen filled glovebox (M. Braun Inertgas-Systeme GmbH, Garchingen, Germany) in silver cups on a ceramic heater up to 550°C.

Crystallographic studies

All data were collected on an Oxford Gemini S diffractometer (Agilent Technologies Sales and Services GmbH and Co. KG, Life Sciences and Chemical Analysis, Waldbronn, Germany) using graphite-monochromatized Cu-Kα radiation (λ=1.54184 Å). The structures of 1, C, D and E were solved by direct methods using SHELXS-2013 and refined by full-matrix least-squares procedures on F2 using SHELXL-2013 (Sheldrick 2013). All non-hydrogen atoms were refined anisotropically. All C-bonded hydrogen atoms were geometrically placed and refined isotropically in riding modes using appropriate SHELXL-2013 HFIX constraints. The positions of Si- and Ge-bonded hydrogen atoms were taken from difference Fourier maps and refined isotropically. Data have been deposited at the Cambridge Crystallographic Data Centre under the CCDC deposition numbers 1526800 (1), 1526803 (C), 1526801 (D) and 1526802 (E).

Due to a phase transition below approximately 160 K the single crystal of D had been measured at 180 K. Due to higher measurement temperature, Uij values especially of the carbon atoms of the Cp* ligands are comparatively large. Trials to refine each of the two independent disordered Cp* rings on two positions failed. Nevertheless, valid results for compound D were obtained. Crystallographic data for A and B were extracted from the cif-files [No. 180860 (A) and No. 1166703 (B)] deposited at the CCDC.

Synthesis of GeH2Cp*2 (1)

Lithium aluminum hydride (0.10 g, 24 mmol) was added in a single portion to a solution of GeCl2Cp*2 (A) (1.00 g, 2.4 mmol) in tetrahydrofuran (30 mL) at −80°C. The grey suspension was stirred for 1.5 h at 20°C, and then the solvent was removed under reduced pressure and n-hexane (30 mL) was added. The suspension was then filtered through celite, and evaporation of n-hexane in vacuum gave a colorless solid. Single crystals suitable for X-ray analysis were grown from a CH3CN solution at −30°C.

Yield: 0.81 g (98%) colorless solid, with mp. 83‒85°C, decomposition 200°C. Elemental analysis (%) calcd. for C18H32Ge (345.11): C, 69.61; H, 9.35; Found: C, 69.34; H, 9.73. EI-MS: m/z 346 [M]+ (1.4%), m/z 209 [C10H15Ge]+ (100%). ATR-FTIR [cm−1]: ν(CH3) 2913 (s), 2857 (s), ν(Ge-H) 2008 (s), 870 (s), 743 (s), 724 (s). 1H NMR (500 MHz, CDCl3): δ 1.70 [s br, 30H C5 (CH3)5], 3.91 [s, 2H, GeH2]. 13CNMR (125 MHz, CDCl3): δ 10.33 [s, C5 (CH3)5], 135.25 [s, C5 (CH3)5].

Acknowledgements

We gratefully acknowledge the BMBF (Project No. 214648), the SMWK (Project No. 4-7531.50/1128/1) and the Fonds der Chemischen Industrie for financial support.

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Received: 2017-3-17
Accepted: 2017-4-10
Published Online: 2017-4-29
Published in Print: 2017-4-1

©2017 Walter de Gruyter GmbH, Berlin/Boston

This article is distributed under the terms of the Creative Commons Attribution Non-Commercial License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

Articles in the same Issue

  1. Frontmatter
  2. Research Articles
  3. Synthesis and characterization of GeH2Cp*2 and its structural comparison with SiXHCp*2(X=Cl, H) and SnCl2Cp*2
  4. Facile synthesis of hexagonal strontium ferrite nanostructures and hard magnetic poly carbonate nanocomposite
  5. Nano-basic silica as an efficient catalyst for the multi-component preparation of pyrano[2,3-d]pyrimidine derivatives
  6. Selective bulk liquid membrane carrier facilitated transport of Mg2+ over Li+, Na+, K+ and Ca2+ metal ions using naphthaquinone derived redox-switchable ionophores
  7. Green synthesis and characterization of flower-like PbS and metal-doped nanostructures via hydrothermal method
  8. Antimony(III) and bismuth(III) complexes containing O- and N-chelating ligands: synthesis, FT-IR, 1H and 13C NMR spectroscopic and mass spectrometric studies
  9. Synthesis and structure of [Na(15-crown-5)][Ph2P(S)OB(C6F5)3] and [Na(15-crown-5)2][Ph2P(S)O···HO(S)PPh2]
  10. Short Communication
  11. Synthesis and structure of the dimericdiorganotinhydroxyphosphinate [t-Bu2Sn(OH)OPPh2O)]2
https://doi.org/10.1515/mgmc-2017-0014
Keywords for this article
crystal structure; decomposition behavior; germanium; pentamethylcyclopentadienyl; silicon; tin
Creative Commons
BY-NC-ND 3.0

Articles in the same Issue

  1. Frontmatter
  2. Research Articles
  3. Synthesis and characterization of GeH2Cp*2 and its structural comparison with SiXHCp*2(X=Cl, H) and SnCl2Cp*2
  4. Facile synthesis of hexagonal strontium ferrite nanostructures and hard magnetic poly carbonate nanocomposite
  5. Nano-basic silica as an efficient catalyst for the multi-component preparation of pyrano[2,3-d]pyrimidine derivatives
  6. Selective bulk liquid membrane carrier facilitated transport of Mg2+ over Li+, Na+, K+ and Ca2+ metal ions using naphthaquinone derived redox-switchable ionophores
  7. Green synthesis and characterization of flower-like PbS and metal-doped nanostructures via hydrothermal method
  8. Antimony(III) and bismuth(III) complexes containing O- and N-chelating ligands: synthesis, FT-IR, 1H and 13C NMR spectroscopic and mass spectrometric studies
  9. Synthesis and structure of [Na(15-crown-5)][Ph2P(S)OB(C6F5)3] and [Na(15-crown-5)2][Ph2P(S)O···HO(S)PPh2]
  10. Short Communication
  11. Synthesis and structure of the dimericdiorganotinhydroxyphosphinate [t-Bu2Sn(OH)OPPh2O)]2
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