The disilanes Cp*SiCl2SiH3 and Cp*SiH2SiH2Cp*

Ronny Fritzsche 1 , Tobias Rüffer 2 , Heinrich Lang 2 ,  and Michael Mehring 1
  • 1 Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Professur Koordinationschemie, D-09107 Chemnitz, Germany
  • 2 Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Professur Anorganische Chemie, D-09107 Chemnitz, Germany
Ronny Fritzsche, Tobias Rüffer, Heinrich Lang and Michael Mehring

Abstract

Hydrogenation of Cp*SiCl2SiCl3 (A) (Cp*=C5Me5) with diisobutylaluminum hydride (DIBAL-H) gave partially hydrogenated disilane Cp*SiCl2SiH3 (1) with 45% yield, whereas the reaction with lithium aluminum hydride (LiAlH4) provided the well-known Cp*SiH2SiH3. The symmetric disilane Cp*SiH2SiH2Cp* (2) is accessible either by hydrogenation of Cp*SiCl2SiCl2Cp* (B) with DIBAL-H or LiAlH4 but attempts to partially hydrogenate the disilane B failed. The reaction of B with 1 eq. DIBAL-H afforded a mixture of five different molecules of the type Cp*SiR1R2SiR3R4Cp* (D, R1-R4=H, Cl) which co-crystallize in a single crystal with a H/Cl ratio of 1/3. Characterization by 1H and 29Si NMR, ATR IR spectroscopy, EI mass spectrometry and for 1 and the co-crystal D the single crystal X-ray diffraction analysis is presented. Compounds 1 and 2 are thermally stable in the solid state and do not decompose prior to evaporation.

Introduction

Silanes bearing the Cp* ligand (Cp*=C5Me5) have been intensively studied in the past. The steric bulkiness of the ligand allowed the isolation of numerous unusual molecules such as SiCp*2, (SiCp*F)4, and [SiCp*]+ [B(C6F5)4]- (Jutzi et al., 1986, 1988a, 2004; Kuehler and Jutzi, 2003). Additional examples reported are the monosilanes SiCp*R′3, SiCp*2R″2 (R′, R″=F, Cl, Br, H, OH; R″=H, Cl; H, Br; H, NH2), and the disilanes Cp*SiR2SiR3 (R=H, Cl) and Cp*SiR2SiR2Cp* (R=Cl, Br, NH2) (Ackerhans et al., 2001; Klipp et al., 2001). Partially hydrogenated disilanes have been less intensively studied and examples such as PhSiCl2SiH3, Ph2ClSiSiH3, and PhHClSiSiH3 (Haas et al., 1993; Uhlig, 1993) are accessible only over multiple reaction steps. One reason might be that hydrogenation of chlorosilanes is challenging because the commonly used reagents lithium aluminum hydride (LiAlH4) or KH easily lead to dismutation reactions or give a full exchange of chlorine for hydrogen (Uhlig, 1993; Fritz et al., 1994; Ackerhans et al., 2001). However, the synthesis of partially hydrogenated silanes starting from chlorosilanes utilizing trialkylstannanes and a Lewis base has been reported (Hengge et al., 1995; Herzog et al., 1996, 1995; Pätzold et al., 1996; Herzog and Roewer, 1997). We decided to test diisobutylaluminum hydride (DIBAL-H) as an alternative hydrogenating reagent because it does not attack Si-Si bonds in oligosilanes, and hydrogenation of chlorosilanes without addition of any catalyst is possible (Cannady and Zhou, 2008). The use of DIBAL-H in organic synthesis is manifold (Winterfeldt, 1975); however, studies concerning hydrogenation of silanes are rare (Fritz et al., 1994; Fritzsche et al., 2014). Here, we demonstrate its use for the synthesis of the new disilanes Cp*SiCl2SiH3 (1) and Cp*SiH2SiH2Cp* (2), and report on attempts to partially hydrogenate Cp*SiCl2SiCl2Cp*.

Results and discussion

Synthesis and characterization

In order to synthesize the disilanes 1 and 2 starting from the corresponding chloro-substituted disilanes, DIBAL-H and LiAlH4 were chosen as hydrogenating agents (Scheme 1). The hydrogenation of Cp*SiCl2SiCl3 (A) with DIBAL-H in excess always leads to the partially hydrogenated silane Cp*SiCl2SiH3 (1), whereas the reaction with an excess of LiAlH4 provided Cp*SiH2SiH3 (C) in accordance with a literature report (Jutzi et al., 2004). The organosilane Cp*SiH2SiH2Cp* (2) was synthesized either by hydrogenation of Cp*SiCl2SiCl2Cp* (B) with 1.1 eq. LiAlH4 or by the use of 4.4 eq. of DIBAL-H. Isolation of the silanes is possible either by crystallization (1 and 2) or sublimation in case of Cp*SiH2SiH2Cp* (2) when synthesized with LiAlH4. Sublimation of silanes 1 and 2 directly from the reaction mixture containing DIBAL-H was not successful, because of the co-condensation of the silane and diisobutylaluminum chloride (DIBAL-Cl). 1H NMR analysis of the silanes Cp*SiCl2SiH3 (1) and Cp*SiH2SiH2Cp* (2) shows the expected signals for the Cp* and SiH groups. However, it is worth to note that in the 1H NMR spectra the signal of silane 1 for the Cp* ligand is a sharp singlet at δ 1.82 ppm, whereas for silane 2 it appears as a rather broad resonance at δ 1.72 ppm, both indicating dynamic behavior as a result of sigmatropic shifts (Jutzi et al., 1988b). The 29Si NMR signals for 1 appear at δ 6.9 ppm which is assigned to the SiCl2 moiety and at δ -90.4 ppm for the SiH3 moiety. This is in agreement with the reported 29Si NMR signals for PhSiCl2SiH3 at δ 16.8 ppm and δ -90.7 ppm (Haas et al., 1993). The 29Si NMR signal for Cp*SiH2SiH2Cp* (2) at δ -38.9 ppm is shifted downfield compared to 1,2-diphenyldisilane (δ 29Si -61.2 ppm) and 1,2-dimesityldisilane (δ 29Si -79.3 ppm) (Söldner et al., 1997).

Scheme 1:
Scheme 1:

Reaction of Cp*-substituted disilanes with diisobutylaluminum hydride (DIBAL-H) and LiAlH4.

Citation: Main Group Metal Chemistry 38, 3-4; 10.1515/mgmc-2015-0015

Motivated by the observation of a selective partial hydrogenation of A, we tried to substitute partially the chlorine atoms in B by the use of 1, 2, and 3 eq. of DIBAL-H. As an example, GC-MS analysis of the reaction mixture was performed after addition of 1 eq. of DIBAL-H to a THF solution of B. The mass fragments indicate that diverse silanes of the type Cp*SiR1R2SiR3R4Cp* were formed (Scheme 1), for example, B m/z 333 [M–Cp*]+ (31%), 3a m/z 299 [M–Cp*]+ (25%), 3b m/z 398 [M]+ (3%); m/z 263 [M–Cp*]+ (35%), 3c m/z 364 [M]+ (3%); m/z 229 [M–Cp*]+ (75%), and 2 m/z 330 [M]+ (2%), m/z 195 [M–Cp*]+ (100%). The abstraction of Cp*, which is observed as the major fragmentation pathway under electron impact, gave the typical fragments [M–Cp*]+. This observation provides evidence that a mixture of 2, 3a-3c, and B was formed upon the reaction of silane B with 1 eq. of DIBAL-H. The same qualitative observation was made upon varying the amount of DIBAL-H and thus we conclude that a partial hydrogenation of silane B cannot be controlled by varying the molar ration of B and DIBAL-H. The separation of the products by crystallization was not successful, instead co-crystals D composed of 2, 3a-3c, and B were obtained. Attempts to crystallize this mixture from Et2O or CH3CN resulted in an enrichment of chlorosilane B, due to the high solubility of the partially hydrogenated silanes in organic solvents, but full separation failed.

In order to test the suitability of the silanes 1 and 2 as CVD precursors, they were heated in an open silver cup in a glovebox under nitrogen atmosphere, resulting in a complete evaporation of the silanes without any residue left in the silver cups, which indicates evaporation prior to decomposition. In addition, differential scanning calorimetry was carried out and evaporation starting from 180°C (1) and 210°C (2) of the silanes and finally a minor portion of a solid decomposition product was observed. Although the silanes are sensitive to air and moisture, they are stable under inert conditions. However, attempts to decompose the silanes in order to produce silicon by atmospheric pressure chemical vapor deposition (APCVD) at 500°C to 550°C failed.

Single crystal X-ray diffraction

Single crystals of silane 1 were obtained from a Et2O/CH3CN (v/v) mixture at -30°C. Crystallographic data are provided in Table 1 and selected bond lengths and angles are given in the caption of Figure 1. The molecular structure of the silane Cp*SiCl2SiH3 (1) (Figure 1) resembles that of previously reported (Me4HC5)Si2Cl5 (E) and (Me4EtC5)Si2Cl5 (F) in terms of its Si-Si 2.3294(15) Å (E 2.336(2) Å; F 2.327(3) Å) and Si-C 1.902(4) Å (E 1.866(2) Å; F 1.893(7) Å) bond lengths (Klipp et al., 2001). The σ Si-Cp* bond and the staggered conformation of the disilanyl group are typical for Cp* substituted disilanes (Klipp et al., 2001). The silicon-hydrogen bond lengths Si(2)-H(1) 1.367(17) Å, Si(2)-H(2) 1.332(18) Å, and Si(2)-H(3) 1.334(18) Å are as expected and correspond to the Si-H bond distances as reported for organosilanes, for example, C6H3-2,6-(CH2OtBu)2SiPhH2 (1.45(2) and 1.50(2) Å) (Novák et al., 2014), [{2,6-bis(diisopropoxyphosphonyl)-4-tert-butyl}phenyl]di-hydridophenylsilane (1.348(15) Å and 1.421(15) Å) (Peveling et al., 2006) and tris(N-methylpyrrol-2-yl)silane (1.386(18) Å) (Fritzsche et al., 2014). The IR bands for the Si-H bond of silane 1 are observed at 2143 cm-1 and 2170 cm-1 indicating symmetrical and asymmetrical Si-H vibrations (Cui and Kertesz, 1992), whereas for 2 only one Si-H band at 2109 cm-1 is observed. Although crystals of Cp*SiH2SiH2Cp* (2) were obtained, they were not suitable for single crystal X-ray diffraction analysis as a result of their polycrystalline nature. However, we did obtain suitable crystals from a reaction mixture of compound B to which 1 eq. of DIBAL-H was added. Slow evaporation gave plate-like crystals that proved to be the co-crystal D comprising 2, 3a-3c, and B. This was independently confirmed by GC-MS analysis of a crystalline fraction. Because co-crystals with multiple entities were rarely reported, here we discuss the refinement in more detail. Crystallographic data are provided in Table 1. Upon solving the structure starting from 3a as model it became obvious that the occupation factors of each individual chlorine atom are far from 1.0. For the following refinement cycles, these occupation factors were allowed to refine without restrains by using the PART instruction to give individual occupation factors in the range from 0.50 to 0.95. Of the remaining electron density peaks in the vicinity (ca. 1.3 Å) of the silicium atoms appropriate ones were selected and assigned as hydrogen atoms. Each individual hydrogen atom was then allowed to refine without restrains with respect to its occupation factor, whereby one chlorine and an appropriate hydrogen atom were summarized by the same PART instruction to give an overall occupation factor of one. For the refinement of the hydrogen atoms DFIX and DANG restraints were applied. After final refinement the chemical formula was ‘C30H46.51Cl4.49Si3’. Keeping in mind that the asymmetric unit of the co-crystal D contains one crystallographic independent ensemble of 2, 3a-3c, and B (comprising the silicium atoms Si1 and Si2) and one (comprising the Si3 atom) with crystallographically imposed inversion symmetry (the inversion center is in the middle of the Si3-Si3A bond) an ideal overall chemical formula of C30H46.50Cl4.50Si3 is expected, which nicely fits to a monohydrogenated product 3a. It should be noted that the entry ‘chemical formula sum’ in the final crystallographic file was not corrected to the ideal formula C30H46.50Cl4.50Si3, and thus, a minor discrepancy remains, however, within expected error margins. Furthermore, it should be noted that Ueq values of the crystallographic independent ensemble of 2, 3a-3c, and B are not conspicuous, whereas those of the ensemble featuring crystallographically imposed inversion symmetry are rather large. Additionally, in close vicinity to the latter comparatively high remaining electron density is observed. Both observations are attributed to the phenomena of the co-crystallization of five different molecules and trials to refine these molecules individually did not give reliable results.

Table 1

Crystallographic data and structure refinement details for compound 1 and co-crystal D composed of 3a-3c, B, 2.

Compound1Co-crystal D
Empirical formulaC10H18Cl2Si2C30H46.51Cl4.49Si3
Formula weight (g/mol)265.32650.53
Temperature (K)110110
Wavelength (Å)0.710730.71073
Crystal systemmonoclinicmonoclinic
Space groupP2(1)/nP2(1)/n
a (Å)9.0593(6)21.147(4)
b (Å)12.2651(8)10.3882(3)
c (Å)12.3851(11)29.066(6)
α (°)9090
β (°)92.134(6)147.19(5)
γ (°)9090
V3)1375.19(18)3460(3)
Z44
Density (calculated) (g/cm3)1.2821.249
Absorption coefficient (mm-1)0.6110.502
F(000)5601379
Crystal size (mm3)0.3×0.3×0.30.34×0.12×0.04
θ Range for data collection3.202–25.0002.913–24.999
Limiting indices-10≤h≤10-24≤h≤25
-13≤k≤14-12≤k≤12
-12≤l≤14-34≤l≤32
Reflections collected493918283
Independent reflections2400 [Rint=0.0220]6042 [Rint=0.0362]
Completeness99.099.1
Refinement methodFull-matrix least-squares on F2Full-matrix least-squares on F2
Data/restraints/parameters2400/6/1396042/333/396
Final R indices [I>2σ(I)]R1=0.0559R1=0.0915
wR2=0.1407wR2=0.2239
R indices (all data)R1=0.0624R1=0.1184
wR2=0.1437wR2=0.2399
Goodness-of-fit on F21.0901.049
Largest diff peak and hole [eÅ-3]0.806 and -0.3252.899 and -1.249
Figure 1:
Figure 1:

ORTEP diagram at 50% probability (Si, Cl, and C) and 20% probability (H) and atom numbering scheme for compound 1. Hydrogen atoms at carbon atoms are omitted for clarity. Selected bond lengths (Å) and angles (°):C(1)-Si(1) 1.902(4), Si(1)-Cl(1) 2.0777(15), Si(1)-Cl(2) 2.0821(15), Si(1)-Si(2) 2.3294(15), Si(2)-H(1) 1.367(17), Si(2)-H(2) 1.332(18), Si(2)-H(3) 1.334(18), C(1)-Si(1)-Cl(1) 110.83(13), C(1)-Si(1)-Cl(2) 109.21(13), Cl(1)-Si(1)-Cl(2) 101.76(6), C(1)-Si(1)-Si(2) 117.50(13), Cl(1)-Si(1)-Si(2) 110.34(6), Cl(2)-Si(1)-Si(2) 105.90(6), Si(1)-Si(2)-H(1) 107.3(17), Si(1)-Si(2)-H(2) 115(2), H(1)-Si(2)-H(2) 112(2), Si(1)-Si(2)-H(3) 103(2), H(1)-Si(2)-H(3) 108(2), H(2)-Si(2)-H(3) 111(2).

Citation: Main Group Metal Chemistry 38, 3-4; 10.1515/mgmc-2015-0015

Conclusion

Diisobutylaluminum hydride allows a selective partial hydrogenation of Cp*SiCl2SiCl3 (A) to give Cp*SiCl2SiH3 (1), in contrast to its reaction with Cp*SiCl2SiCl2Cp* (B). If used in excess, the fully hydrogenated compound Cp*SiH2SiH2Cp* (2) is available, whereas the use of 1 to 3 eq. of DIBAL-H provides mixtures of 2, 3a-3c, and B. The latter tend to crystallize as co-crystals containing all types of possible hydrogenation products together with the starting material B. Compounds 1 and 2 show high thermal stability and evaporate before thermal decomposition if exposition to air and moisture is rigorously excluded, and do not decompose to give silicon at temperatures below 550°C. Please note that the reactivity of DIBAL-H described here might offer the possibility to hydrogenate terminal SiCl3 groups in oligosilanes.

Experimental

General procedure

All reactions were carried out under an argon atmosphere using standard Schlenk techniques or a Glovebox under nitrogen atmosphere. The synthesis of Cp*SiCl2SiCl3 (A) and Cp*SiCl2SiCl2Cp* (B) was carried out according to literature methods (Jutzi et al., 1986; Ackerhans et al., 2001). THF was dried by distillation from sodium-potassium alloy. CH3CN was dried by distillation from CaH2. All other chemicals were purchased from commercial suppliers. LiAlH4 (Alfa Aesar 97%, Ward Hill, MA, USA) and DIBAL-H (Aldrich 97%, Sigma-Aldrich Corp. St. Louis, MO, USA) were used as received. ATR-FT-IR spectra were measured with a BioRad FT-IR 165 spectrometer (Bio-Rad Laboratories, Philadelphia, PA, USA) with Golden Gate ATR (LOT-Oriel GmbH & 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}, 99 MHz for 29Si{1H}). 29Si NMR Spectra were recorded inverse gate decoupled. 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); however, the elemental analyses were not fully in accordance with the calculated values as a result of the high air and moisture sensitivity of compounds 1 and 2. The melting points (sealed off in argon flushed capillaries) were determined using a Büchi Melting Point B-540 (Buchi Labortechnik GmbH, Essen, Germany). DSC measurements were carried out with a Mettler Toledo DSC 1 (Mettler-Toledo GmbH, Gießen, Germany) in 40 μL Al cups under nitrogen with a flow rate of 50 mL min-1 and a heating rate of 10 K min-1. EI MS was performed with a Shimadzu GC-17A Gas Chromatograph and GC-MS-QP5000 Gas Chromatograph Mass Spectrometer (Shimadzu Corp, Kyōto, Japan).

Crystallographic studies

All data were collected on an Oxford Gemini S diffractometer (Agilent Technologies Sales & Services GmbH & Co. KG, Life Sciences & Chemical Analysis, Waldbronn, Germany) using graphite-monochromatized Mo Ka radiation (l=0.71073 Å). All structures 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 default SHELXTL parameters. In case of silane 1 the hydrogen atoms at all respective methyl groups were calculated as idealized disordered methyl groups on two positions. The positions of Si-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 1059810 (1) and 1059811 (D).

Synthesis of 1,1-dichloro-1-(pentamethylcyclopentadienyl)disilane (Cp*SiCl2SiH3) (1)

A solution of DIBAL-H (5.12 g, 36 mmol) in THF (30 mL) was dropped to a solution of Cp*SiCl2SiCl3 (A) (4.00 g, 11 mmol) in THF (30 mL) at room temperature and was then heated at reflux for 24 h. After THF was removed under reduced pressure, CH3CN (20 mL) was slowly added to the cloudy viscous oil. Cooling the solution for 24 h to -30°C afforded colorless crystals, which were crystallized three times from CH3CN and then dried under vacuum.

Yield: 1.3 g (45%) colorless solid, with mp 50°C to 51°C. EI-MS: m/z 264 [M]+ (7%), m/z 233 [M–SiH3]+ (6%), m/z 135 [C10H15]+ (100%). ATR-IR [cm-1]: ν (SiH): 2143 (s); ν (SiH): 2170 (s); ν (CH3): 2869 (m); ν (CH3): 2913 (m); ν (CH3): 2965 (m). 1H NMR (500 MHz, CDCl3): δ 1.82 [s, 15H], 2.96 [s, 3H, -SiH3], 13C{1H} NMR (125 MHz, CDCl3): δ 11.3 [s, -CH3]. 29Si{1H} NMR (99 MHz, CDCl3): δ 6.9 [s, SiCl2], δ -90.1 [s, SiH3].

Synthesis of 1,2-di(1,2,3,4,5-pentamethylcyclopentadienyl)disilane (Cp*SiH2SiH2Cp*) (2)

Method A The disilane Cp*SiCl2SiCl2Cp* (B) (0.70 g, 1.5 mmol) was dissolved in THF (5 mL). To this solution DIBAL-H (0.94 g, 6.6 mmol) was added in a single portion at room temperature and the mixture was stirred for 1.5 h. After THF was removed under reduced pressure, CH3CN (10 mL) was slowly added to the viscous oil. Cooling the solution for 24 h to -30°C afforded colorless needles which were washed three times with cold CH3CN (5 mL) and then dried under vacuum. Yield: 0.22 g (45%) colorless solid with mp 141°C to 143°C.

Method B The disilane Cp*SiCl2SiCl2Cp* (B) (0.70 g, 1.5 mmol) was dissolved in THF (30 mL). LiAlH4 (powder, 0.17 g, 4.4 mmol) was added at -80°C in a single portion and the gray suspension was stirred for 1.5 h. The solvent was removed under reduced pressure and n-hexane (30 mL) was added. The suspension was then filtered through Celite. After crystallization from CH3CN at -30°C, a colorless solid was obtained. Yield: 0.43 g (86%) colorless solid with mp 142°C to 144°C. EI-MS: m/z 330 [M]+ (2%), m/z 195 [M–C10H15]+ (100%). ATR-IR [cm-1]: ν (SiH): 2109 (s); ν (CH3): 2863 (m); ν (CH3): 2910 (m); ν (CH3): 2950 (m). 1H NMR (500 MHz, CDCl3): δ 1.72 [m, 30H], 3.1 [s, 4H, –SiH2], 13C{1H} NMR (125 MHz, CDCl3): δ 10.1 [m, –CH3], 135.2 [m, C-CH3]. 29Si{1H} NMR (99 MHz, CDCl3): δ -38.9 [s, SiH2].

Partial hydrogenation of Cp*SiCl2SiCl2Cp*

The disilane Cp*SiCl2SiCl2Cp* (B) 0.10 g (0.21 mmol) was dissolved in THF (4 mL) and a solution of DIBAL-H (1 eq., 0.03 g, 0.21 mmol) (3a) in THF (2 mL) was added at room temperature. The mixture was stirred overnight at 70°C. Slow evaporation of the solvent afforded colorless crystals suitable for single crystal X-ray diffraction analysis. EI-MS: 3a (R1=R2=R3=Cl; R4=H) m/z 299 [M–cp*]+ (25%); m/z 135 [cp*]+ (100%), 3b (R1=R2=Cl; R3=R4=H) m/z 398 [M]+ (3%); m/z 263 [M–cp*]+ (35%); m/z 263 [SiH2Cp*]+ (100%)}, 3c (R1=Cl; R2=R3=R4=H) m/z 364 [M]+ (3%); m/z 229 [M–cp*]+ (75%); m/z 163 [SiCp*]+ (100%).

Acknowledgments

We are grateful to the Bundesministerium für Bildung und Forschung (BMBF; Project No. 214648), the Sächsisches Staatsministerium für Wissenschaft und Kunst (SMWK), German Academic Exchange Service London Office, and the Fonds der Chemischen Industrie for financial support.

References

  • Ackerhans, C.; Boettcher, P.; Mueller, P.; Roesky, H. W.; Uson, I.; Schmidt, H.-G.; Noltemeyer, M. Halogenodisilanes: precursors for new disilane derivatives. Inorg. Chem. 2001, 40, 3766–3773.

  • Cannady, J. P.; Zhou, X. Composition comprising neopentasilane and method of preparing same. 2008, WO2008051328A2008051321.

  • Cui, C. X.; Kertesz, M. Assignment of the vibrational spectra of polysilane and its oligomers. Macromolecules 1992, 25, 1103–1108.

  • Fritz, G.; Lauble, S.; Breining, M.; Beetz, A. G.; Galminas, A. M.; Matern, E.; Goesmann, H. Bildung siliciumorganischer Verbindungen. 111. Die Hydrierung Si-chlorierter, C-spiroverbrückter 2,4-Disilacyclobutane mit LiAlH4 und iBu2AlH. Der Zugang zum Si8C3H20. Z. Anorg. Allg. Chem. 1994, 620, 127–135.

  • Fritzsche, R.; Seidel, F.; Rueffer, T.; Buschbeck, R.; Jakob, A.; Freitag, H.; Zahn, D. R. T.; Lang, H.; Mehring, M. New organosilanes based on N-methylpyrrole – synthesis, structure and characterization. J. Organomet. Chem. 2014, 755, 86–92.

  • Haas, A.; Suellentrup, R.; Krueger, C. Synthesis and characterization of new cyclic and acyclic silachalcogenanes with disilanyl units. Z. Anorg. Allg. Chem. 1993, 619, 819–826.

  • Hengge, E.; Grogger, C.; Uhlig, F.; Roewer, G.; Herzog, U.; Pätzold, U. Hydrierung von Silicium-Halogen-Verbindungen mittels Trialkylstannylchlorid/Natriumhydrid. Monatsh. Chem. 1995, 126, 549–555.

  • Herzog, U.; Roewer, G. Base catalysed hydrogenation of methylbromooligosilanes with trialkylstannanes, identification of the first methylbromohydrogenoligosilanes. J. Organomet. Chem. 1997, 527, 117–124.

  • Herzog, U.; Roewer, G.; Pätzold, U. Katalytische hydrierung chlorhaltiger disilane mit tributylstannan. J. Organomet. Chem. 1995, 494, 143–147.

  • Herzog, U.; Brendler, E.; Roewer, G. Basekatalysierte hydrierung von methylchlortri- und -tetrasilanen mit trialkylstannanen zu methylchlorwasserstofftri- und -tetrasilanen. J. Organomet. Chem. 1996, 511, 85–91.

  • Jutzi, P.; Holtmann, U.; Boegge, H.; Mueller, A. Protonation of decamethylsilicocene [bis(pentamethylcyclopentadienyl)silicon]. J. Chem. Soc. Chem. Commun. 1988a, 305–306.

  • Jutzi, P.; Kanne, D.; Hursthouse, M.; Howes, A. J. Mono- and bis(η1-pentamethylcyclopentadienyl)silanes. Synthesis, structure, and properties. Chem. Ber. 1988b, 121, 1299–1305.

  • Jutzi, P.; Kanne, D.; Kruger, C. Decamethylsilicocene-synthesis and structure. Angew. Chem. 1986, 98 , 163–164.

  • Jutzi, P.; Mix, A.; Rummel, B.; Schoeller, W. W.; Neumann, B.; Stammler, H.-G. The (Me5C5)Si+ Cation: a stable derivative of HSi+. Science 2004, 305, 849–851.

  • Klipp, A.; Petri, S. H. A.; Neumann, B.; Stammler, H. G.; Jutzi, P. Novel cyclopentadienyl silanes and disilanes: synthesis, structure and gas-phase pyrolysis. J. Organomet. Chem. 2001, 620, 20–31.

  • Kuehler, T.; Jutzi, P. Decamethylsilicocene: synthesis, structure, bonding and chemistry. Adv. Organomet. Chem. 2003, 49, 1–34.

  • Novák, M.; Dostál, L.; Padělková, Z.; Jurkschat, K.; Dietz, C.; Růžička, K.; Fulem, M.; Lyčka, A.; Jambor, R. Organohydridosilanes containing Y,C,Y-chelating ligands: reactivity and vapour pressure studies. J. Organomet. Chem. 2014, 772–773, 1–6.

  • Pätzold, U.; Roewer, G.; Herzog, U. Katalytische hydrierung von halogenmonosilanen mit tributylzinnhydrid. J. Organomet. Chem. 1996, 508, 147–152.

  • Peveling, K.; Dannappel, K.; Schürmann, M.; Costisella, B.; Jurkschat, K. Structure-directing properties of lithium chloride in supramolecular {4-t-Bu-2,6-[P(O)(OEt)2]2C6H2}SiH2Ph·LiCl·2H2O. Intermolecular PO→Li versus intramolecular PO→(H)Si coordination. Organometallics 2006, 25, 368–374.

  • Sheldrick, G. M. SHELXS-/SHELXL-2013, University of Göttingen, Program for Crystal Structure Solution/Refinement, 2013.

  • Söldner, M.; Sandor, M.; Schier, A.; Schmidbaur, H. Synthesis, structure, and photoluminescence of 1,2-disila-acenaphthene Si2C10H10 and 1,2-diaryldisilane reference compounds. Chem. Ber. 1997, 130, 1671–1676.

  • Uhlig, W. Synthesis of functional substituted disilanes on the basis of triflate derivatives. Z. Anorg. Allg. Chem. 1993, 619, 1479–1482.

  • Winterfeldt, E. Applications of diisobutylaluminium hydride (DIBAH) and triisobutylaluminium (TIBA) as reducing agents in organic synthesis. Synthesis 1975, 1975, 617–630.

    • Crossref
    • Export Citation

If the inline PDF is not rendering correctly, you can download the PDF file here.

  • Ackerhans, C.; Boettcher, P.; Mueller, P.; Roesky, H. W.; Uson, I.; Schmidt, H.-G.; Noltemeyer, M. Halogenodisilanes: precursors for new disilane derivatives. Inorg. Chem. 2001, 40, 3766–3773.

  • Cannady, J. P.; Zhou, X. Composition comprising neopentasilane and method of preparing same. 2008, WO2008051328A2008051321.

  • Cui, C. X.; Kertesz, M. Assignment of the vibrational spectra of polysilane and its oligomers. Macromolecules 1992, 25, 1103–1108.

  • Fritz, G.; Lauble, S.; Breining, M.; Beetz, A. G.; Galminas, A. M.; Matern, E.; Goesmann, H. Bildung siliciumorganischer Verbindungen. 111. Die Hydrierung Si-chlorierter, C-spiroverbrückter 2,4-Disilacyclobutane mit LiAlH4 und iBu2AlH. Der Zugang zum Si8C3H20. Z. Anorg. Allg. Chem. 1994, 620, 127–135.

  • Fritzsche, R.; Seidel, F.; Rueffer, T.; Buschbeck, R.; Jakob, A.; Freitag, H.; Zahn, D. R. T.; Lang, H.; Mehring, M. New organosilanes based on N-methylpyrrole – synthesis, structure and characterization. J. Organomet. Chem. 2014, 755, 86–92.

  • Haas, A.; Suellentrup, R.; Krueger, C. Synthesis and characterization of new cyclic and acyclic silachalcogenanes with disilanyl units. Z. Anorg. Allg. Chem. 1993, 619, 819–826.

  • Hengge, E.; Grogger, C.; Uhlig, F.; Roewer, G.; Herzog, U.; Pätzold, U. Hydrierung von Silicium-Halogen-Verbindungen mittels Trialkylstannylchlorid/Natriumhydrid. Monatsh. Chem. 1995, 126, 549–555.

  • Herzog, U.; Roewer, G. Base catalysed hydrogenation of methylbromooligosilanes with trialkylstannanes, identification of the first methylbromohydrogenoligosilanes. J. Organomet. Chem. 1997, 527, 117–124.

  • Herzog, U.; Roewer, G.; Pätzold, U. Katalytische hydrierung chlorhaltiger disilane mit tributylstannan. J. Organomet. Chem. 1995, 494, 143–147.

  • Herzog, U.; Brendler, E.; Roewer, G. Basekatalysierte hydrierung von methylchlortri- und -tetrasilanen mit trialkylstannanen zu methylchlorwasserstofftri- und -tetrasilanen. J. Organomet. Chem. 1996, 511, 85–91.

  • Jutzi, P.; Holtmann, U.; Boegge, H.; Mueller, A. Protonation of decamethylsilicocene [bis(pentamethylcyclopentadienyl)silicon]. J. Chem. Soc. Chem. Commun. 1988a, 305–306.

  • Jutzi, P.; Kanne, D.; Hursthouse, M.; Howes, A. J. Mono- and bis(η1-pentamethylcyclopentadienyl)silanes. Synthesis, structure, and properties. Chem. Ber. 1988b, 121, 1299–1305.

  • Jutzi, P.; Kanne, D.; Kruger, C. Decamethylsilicocene-synthesis and structure. Angew. Chem. 1986, 98 , 163–164.

  • Jutzi, P.; Mix, A.; Rummel, B.; Schoeller, W. W.; Neumann, B.; Stammler, H.-G. The (Me5C5)Si+ Cation: a stable derivative of HSi+. Science 2004, 305, 849–851.

  • Klipp, A.; Petri, S. H. A.; Neumann, B.; Stammler, H. G.; Jutzi, P. Novel cyclopentadienyl silanes and disilanes: synthesis, structure and gas-phase pyrolysis. J. Organomet. Chem. 2001, 620, 20–31.

  • Kuehler, T.; Jutzi, P. Decamethylsilicocene: synthesis, structure, bonding and chemistry. Adv. Organomet. Chem. 2003, 49, 1–34.

  • Novák, M.; Dostál, L.; Padělková, Z.; Jurkschat, K.; Dietz, C.; Růžička, K.; Fulem, M.; Lyčka, A.; Jambor, R. Organohydridosilanes containing Y,C,Y-chelating ligands: reactivity and vapour pressure studies. J. Organomet. Chem. 2014, 772–773, 1–6.

  • Pätzold, U.; Roewer, G.; Herzog, U. Katalytische hydrierung von halogenmonosilanen mit tributylzinnhydrid. J. Organomet. Chem. 1996, 508, 147–152.

  • Peveling, K.; Dannappel, K.; Schürmann, M.; Costisella, B.; Jurkschat, K. Structure-directing properties of lithium chloride in supramolecular {4-t-Bu-2,6-[P(O)(OEt)2]2C6H2}SiH2Ph·LiCl·2H2O. Intermolecular PO→Li versus intramolecular PO→(H)Si coordination. Organometallics 2006, 25, 368–374.

  • Sheldrick, G. M. SHELXS-/SHELXL-2013, University of Göttingen, Program for Crystal Structure Solution/Refinement, 2013.

  • Söldner, M.; Sandor, M.; Schier, A.; Schmidbaur, H. Synthesis, structure, and photoluminescence of 1,2-disila-acenaphthene Si2C10H10 and 1,2-diaryldisilane reference compounds. Chem. Ber. 1997, 130, 1671–1676.

  • Uhlig, W. Synthesis of functional substituted disilanes on the basis of triflate derivatives. Z. Anorg. Allg. Chem. 1993, 619, 1479–1482.

  • Winterfeldt, E. Applications of diisobutylaluminium hydride (DIBAH) and triisobutylaluminium (TIBA) as reducing agents in organic synthesis. Synthesis 1975, 1975, 617–630.

    • Crossref
    • Export Citation
OPEN ACCESS

Journal + Issues

Main Group Metal Chemistry is committed to the publication of studies addressing the theoretical, spectroscopic, mechanistic and synthetic aspects of inorganic, coordination and organometallic main group metal and semi-metal compounds, inlucing zinc, cadmium and mercury. The journal also publishes studies relating to environmental aspects of these metals, their toxicology, release pathways and fate.

Search

  • View in gallery

    Reaction of Cp*-substituted disilanes with diisobutylaluminum hydride (DIBAL-H) and LiAlH4.

  • View in gallery

    ORTEP diagram at 50% probability (Si, Cl, and C) and 20% probability (H) and atom numbering scheme for compound 1. Hydrogen atoms at carbon atoms are omitted for clarity. Selected bond lengths (Å) and angles (°):C(1)-Si(1) 1.902(4), Si(1)-Cl(1) 2.0777(15), Si(1)-Cl(2) 2.0821(15), Si(1)-Si(2) 2.3294(15), Si(2)-H(1) 1.367(17), Si(2)-H(2) 1.332(18), Si(2)-H(3) 1.334(18), C(1)-Si(1)-Cl(1) 110.83(13), C(1)-Si(1)-Cl(2) 109.21(13), Cl(1)-Si(1)-Cl(2) 101.76(6), C(1)-Si(1)-Si(2) 117.50(13), Cl(1)-Si(1)-Si(2) 110.34(6), Cl(2)-Si(1)-Si(2) 105.90(6), Si(1)-Si(2)-H(1) 107.3(17), Si(1)-Si(2)-H(2) 115(2), H(1)-Si(2)-H(2) 112(2), Si(1)-Si(2)-H(3) 103(2), H(1)-Si(2)-H(3) 108(2), H(2)-Si(2)-H(3) 111(2).