NOVEL PERCHLORINATED DISILENES AND GERMASILENES AND ALSO NEOPENTATETRELANES, A METHOD FOR THE PREPARATION THEREOF AND USE THEREOF

Abstract

The invention provides disilenes, germasilenes and neopentatetrelanes, a method for the preparation thereof and use thereof.

Claims

1. A neopentatetrelane of the general formula C ##STR00004## wherein each independently in pairs E is Si or Ge; E′ is C, Si, or Ge; and R is Cl, Me, Et, or Ph.

2. A method for preparing the neopentatetrelane C of claim 1, comprising: (a) dissolving a salt [X.sub.4N]- or [X.sub.4P]-tris(trichlorosilyl)tetrelide in a solvent, wherein the radical X is at least one selected from the group consisting of Me, Et, iPr, nBu, and Ph, wherein the tris(trichlorosilyl)tetrelide has the general formula A.sup.− ##STR00005## where wherein E=Si or Ge; (b) reacting the tris(trichlorosilyl)tetrelide dissolved in step (a) with a Lewis acid to produce a disilene or germasilene having the general formula B ##STR00006## wherein E=Si or Ge; and (c) reacting the disilene or germasilene B with a tetrel chloride R.sub.3E′-Cl at a temperature of −80° C. to 40° C. to obtain the neopentatetrelane C, wherein E′=C, Si, or Ge, and R=Cl, Me, Et, or Ph; or (d) contacting the tris(trichlorosilyl)tetrelide dissolved in step (a) with a suspension at a temperature of −80° C. to 40° C. comprising a Lewis acid, a tetrel chloride R.sub.3E′-Cl, and a solvent to obtain the neopentatetrelane C, wherein E′=C, Si, or Ge, and R=Cl, Me, Et, or Ph.

3. The method of claim 2, wherein the steps (b) and (c), or the step (d), are or is carried out at room temperature.

4. The method of claim 2, wherein the solvent used in step (a) and/or in step (d) is at least one independently selected from the group consisting of dichloromethane, benzene, C.sub.6D.sub.6, And CD.sub.2Cl.sub.2.

5. The method of claim 2, wherein X=nBu.

6. The method of claim 2, wherein the Lewis acid in step (b) or (d) is AlCl.sub.3.

7. The method of claim 2, wherein the step (d) the steps (b) and (c) are each carried out with mixing, the method further comprising after step (d) or (c) removing the solvent over a total period of 1 to 24 hours to extract the neopentatetrelane C.

8. A compound of the general formula B, ##STR00007## wherein E=Si or Ge, prepared by a method comprising: (a) dissolving a salt [X.sub.4N]- or [X.sub.4P]-tris(trichlorosilyl)tetrelide in a solvent, wherein the radical X is at least one selected from the group consisting of Me, Et, iPr, nBu, and Ph, wherein the tris(trichlorosilyl)tetrelide has the general formula A.sup.− ##STR00008## wherein E=Si or Ge, (b) reacting the tris(trichlorosilyl)tetrelide dissolved in step (a) with a Lewis acid and an anthracene or an anthracene derivative to obtain the compound of the general formula B.

9. A GeSi layer, comprising the neopentatetrelane C of claim 1.

Description

EXAMPLE 1: PREPARATION OF NEOPENTATETRELANE (C) WHERE E-SI, R-CL AND E′-GE

[0044] A solution of 0.361 g or 0.535 mmol corresponding to 1.0 eq of [nBu.N][(Cl.sub.3Si).sub.3Si] in 6 ml of CH.sub.2Cl.sub.2 solvent was added dropwise to a suspension of 0.073 g or 0.547 mmol corresponding to 1.0 eq of AlCl.sub.3 and 0.144 g or 0.671 mmol corresponding to 1.3 eq of GeCl.sub.4 in 5 ml of CH.sub.2Cl.sub.2 solvent, until all the solid had dissolved. An orange-coloured solution was obtained which was stirred for 12 hours under ambient conditions.

[0045] The solvent was removed at atmospheric pressure and the orange-coloured solid was removed with 3×10 ml of n-hexane. This gave 0.193 g or 0.316 mmol, corresponding to a proportion of 59% neopentatetrelane (C) as a colourless liquid.

[0046] The .sup.29Si-NMR spectrum of this example is shown in FIG. 1.

[0047] Results of a .sup.1H, .sup.13C and .sup.29Si NMR spectroscopic analysis:

[0048] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2):

[0049] δ=−0.25 ((Cl.sub.3Si).sub.3SiGeCl.sub.3), −32.1 ppm ((Cl.sub.3Si).sub.3SiGeCl.sub.3)

[0050] Hydrogenation of this Neopentatetrelane.

[0051] In a melt-sealable NMR tube, 0.55 ml of a 1M solution of (iBu.sub.2)AlH in C.sub.6H.sub.12, which corresponds to 0.08 g or 0.55 mmol and thus 14.0 eq of (iBu.sub.2)AlH, and 0.25 ml Et.sub.2O were added to 0.02 g or 0.04 mmol corresponding to 1.0 eq of neopentatetrelane.

[0052] After 42 hours, the colourless solution was investigated by NMR spectroscopy. Results:

[0053] .sup.1H NMR (500.2 MHz, C.sub.6H.sub.12): δ=3.36 ppm (q, .sup.4J.sub.HH=7.0 Hz, (H.sub.3Si).sub.3SiGeH.sub.3);

[0054] .sup.29Si NMR (99.4 MHz, C.sub.6H.sub.12): δ=−95.4 ppm (q, .sup.1J.sub.Si-F=200 Hz, (H.sub.3Si).sub.3SiGeH.sub.3);

[0055] .sup.1H/.sup.29Si HSQC-NMR (500.2/99.4 MHz, C.sub.6H.sub.12): δ=3.36/−95.4 ppm;

[0056] .sup.1H/.sup.29Si HMBC-NMR (500.2/99.4 MHz, C.sub.6H.sub.12): δ=3.36/−95.4, 3.36/−136.9 ppm.

EXAMPLE 2: PREPARATION OF NEOPENTATETRELANE (C) WHERE E-E′=SI, UND R-ME

[0057] A solution of 0.238 g or 0.353 mmol corresponding to 1.0 eq of [nBu.sub.4N][(Cl.sub.3Si)Si] in 3 ml of CH.sub.2Cl.sub.2 solvent was added dropwise to a suspension of 0.049 g or 0.367 mmol corresponding to 1.0 eq of AlCl.sub.3 and 0.073 g or 0.672 mmol corresponding to 1.9 eq of Me.sub.3SiCl in 1 ml of CH.sub.2Cl.sub.2 solvent, until all the solid had dissolved. A colourless solution was obtained.

[0058] The solvent was removed with stirring at atmospheric pressure and the colourless solid was extracted with 3×3 ml of n-hexane. This gave 0.134 g or 0.266 mmol, corresponding to a proportion of 75% neopentatetrelane (C) as a colourless crystalline solid.

[0059] The .sup.29Si-NMR spectrum of this example is shown in FIG. 2.

[0060] Results of a .sup.1H, .sup.13C and .sup.29Si NMR spectroscopic analysis:

[0061] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2): δ=10.5 ppm (s, (Cl.sub.3).sub.3SiSiMe.sub.3), −3.5 ppm (sext., .sup.2J.sub.H,Si=7.0 Hz, (Cl.sub.3Si).sub.3SiSiMe.sub.3), −83.5 ppm (m, (Cl.sub.3Si)SiSiMe.sub.3).

[0062] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2): δ=0.58 ppm;

[0063] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2): δ=0.4 ppm;

[0064] .sup.1H/.sup.13C HSQC NMR (500.2/125.8 MHz, CD.sub.2Cl.sub.2): δ=0.58/0.4 ppm;

[0065] .sup.1H/.sup.29Si HMBC NMR (500.2/99.4 MHz, CD.sub.2Cl.sub.2): δ=0.58/−3.5, 0.58/−83.5 ppm.

EXAMPLE 3: PREPARATION OF NEOPENTATETRELANE (C), WHERE E-GE, E′-SI, AND R=ME

[0066] In a melt-sealed NMR tube, 0.100 g or 0.139 mmol corresponding to 1.0 eq of [nBu.sub.4N][(Cl.sub.3Si).sub.3Ge],

[0067] 0.019 g or 0.142 mmol corresponding to 1.0 eq of AlCl.sub.3 and

[0068] 0.093 g or 0.856 mmol corresponding to 6.2 eq of Me.sub.3SiCl

[0069] were reacted in 0.8 ml of CD.sub.2Cl.sub.2 solvent, whereby a yellow solution with orange coloured solid was obtained.

[0070] The solvent was removed at atmospheric pressure and the solid was isolated with 3×3 ml of boiling n-hexane. This gave 0.073 g or 0.133 mmol, corresponding to a proportion of 96% neopentatetrelane (C) where E=Ge, E′=Si, and R=Me.

[0071] The .sup.29Si-NMR spectrum of this example is shown in FIG. 3.

[0072] Results of a .sup.1H, .sup.13C and .sup.29Si NMR spectroscopic analysis:

[0073] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2): δ=9.9 ppm (s, (Cl.sub.3Si).sub.3GeSiMe.sub.3),

[0074] 7.2 ppm (sext., .sup.2J.sub.H,Si=7.0 Hz, (Cl.sub.3Si).sub.3GeSiMe.sub.3).

[0075] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2): δ=0.61 ppm;

[0076] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2): δ=1.2 ppm;

[0077] .sup.1H/.sup.13C HSQC NMR (500.2/125.8 MHz, CD.sub.2Cl.sub.2): δ=0.61/1.2 ppm;

[0078] .sup.1H/.sup.29Si HMBC NMR (500.2/99.4 MHz, CD.sub.2Cl.sub.2): δ=0.61/7.0 ppm.

EXAMPLE 4: PREPARATION OF NEOPENTATETRELANE (C), WHERE E-GE, E′-SI, AND R-ET

[0079] In a melt-sealed NMR tube, 0.10 g or 0.14 mmol corresponding to 1.0 eq of [nBu.sub.4N][(Cl.sub.3Si).sub.3Ge],

[0080] 0.02 g or 0.14 mmol corresponding to 1.0 eq of AlCl.sub.3 and

[0081] 0.13 ml or 0.12 g corresponding to 5.6 eq of Et.sub.3SiCl

[0082] were reacted in 0.8 ml of CD.sub.2Cl.sub.2 solvent, whereby a yellow solution was obtained.

[0083] The solvent was removed at atmospheric pressure.

[0084] By means of subsequent extraction with 3×3 ml of boiling n-hexane, removal of the solvent and Et.sub.3SiCl, this gave 0.08 g or 0.14 mmol corresponding to a proportion of 97% neopentatetrelane (C) where E=Ge, E′=Si, and R=Et as a pale yellow solid.

[0085] The .sup.29Si-NMR spectrum of this example is shown in FIG. 4.

[0086] Results of a .sup.1H, .sup.13C and .sup.29Si NMR spectroscopic analysis:

[0087] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2): δ=21.4 ppm (m, (Cl.sub.3Si).sub.3GeSiCH.sub.2CH.sub.3), 10.7 ppm (s,

[0088] (Cl.sub.3Si).sub.3GeSiCH.sub.2CH.sub.3).

[0089] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2): δ=1.14 ppm (m, (Cl.sub.3Si).sub.3GeSiCH.sub.2CH.sub.3);

[0090] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2): δ=8.4 ((Ca.sub.3Si).sub.3GeSiCH.sub.2CH.sub.3), 6.5 ppm ((Cl.sub.3Si).sub.3GeSiCH.sub.2CH.sub.3);

[0091] .sup.1H/.sup.13C HMBC NMR (500.2/125.8 MHz, CD.sub.2Cl.sub.2): δ=1.14/8.4, 1.14/6.5 ppm;

[0092] .sup.1H/.sup.29Si HMBC NMR (500.2/99.4 MHz, CD.sub.2Cl.sub.2): δ=1.14/21.4 ppm.

EXAMPLE 5: PREPARATION OF NEOPENTATETRELANE (C), WHERE E=GE, E′-C, AND R=PH

[0093] In a melt-sealed NMR tube, 0.080 g or 0.111 mmol corresponding to 1.0 eq of [nBu.sub.4N][(Cl.sub.3Si).sub.3Ge],

[0094] 0.015 g or 0.112 mmol corresponding to 1.0 eq of AlCl.sub.3 and

[0095] 0.031 g or 0.111 mmol corresponding to 1.0 eq of Ph.sub.3CCl

[0096] were reacted in 0.7 ml of CD.sub.2Cl.sub.2 solvent, whereby a yellow solution with yellow solid was obtained.

[0097] The solvent was removed at atmospheric pressure.

[0098] By means of extraction with 3×3 ml of boiling n-hexane and subsequent crystallization, neopentatetrelane (C) where E=Ge, E′=C, and R=Ph was obtained in the form of yellow crystals.

[0099] The .sup.29Si {.sup.1H}-NMR spectrum of this example is shown in FIG. 5A. FIG. 5B shows the crystal structure of this neopentatetrelane.

[0100] Results of a .sup.1H, .sup.13C and ° Si NMR spectroscopic analysis:

[0101] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2): δ=8.2 ppm.

[0102] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2): δ=7.38-7.28 ppm (m, (Cl.sub.3Si).sub.3GeCPh.sub.3),

[0103] δ=7.16-7.12 ppm (m, 2H, (Cl.sub.3Si).sub.3GeCPh.sub.3);

[0104] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2): δ=144.3 ((Cl.sub.3Si).sub.3GeCPh.sub.3(-ipso)),

[0105] 131.4 ((Cl.sub.3Si).sub.3GeCPh.sub.3(-ortho)), 129.8 ((Cl.sub.3Si).sub.3GeCPh.sub.3(-para)),

[0106] 128.2 ((Cl.sub.3Si).sub.3GeCPh.sub.3(-metha)), 70.3 ppm ((Cl.sub.3Si).sub.3GeCPh.sub.3);

[0107] .sup.1H/.sup.13C HMBC NMR (500.2/125.8 MHz, CD.sub.2Cl.sub.2):

[0108] δ=7.38-7.28/144.3, 7.38-7.28/131.4, 7.38-7.28/129.8, 7.38-7.28/128.2, 7.16-7.12/7.16-7.12/144.3, 7.16-7.12/131.4, 7.16-7.12/129.8, 7.16-7.12/128.2, 7.16-7.12/70.3 ppm;

[0109] .sup.1H/.sup.29Si HMBC NMR (500.2/99.4 MHz, CD.sub.2Cl.sub.2): δ=7.16-7.12/8.2 ppm.

EXAMPLE 6: PREPARATION OF NEOPENTATETRELANE (C), WHERE E-GE, E′-SI, AND R=PH

[0110] In a melt-sealed NMR tube, 0.100 g or 0.139 mmol corresponding to 1.0 eq of [nBu.sub.4N][(Cl.sub.3Si).sub.3Ge],

[0111] 0.019 g or 0.142 mmol corresponding to 1.0 eq of AlCl.sub.3 and

[0112] 0.041 g or 0.139 mmol corresponding to 1.0 eq of Ph.sub.3SiCl

[0113] were reacted in 0.8 ml of CD.sub.2Cl.sub.2 solvent, whereby a yellow solution with yellow solid was obtained.

[0114] The solvent was removed at atmospheric pressure.

[0115] By means of extraction with 3×3 ml of boiling n-hexane and subsequent crystallization, neopentatetrelane (C) where E=Ge, E′=Si, and R=Ph was isolated in the form of yellow crystals.

[0116] The .sup.29Si-NMR spectrum of this example is shown in FIG. 6A. FIG. 6B shows the crystal structure of this neopentatetrelane.

[0117] Results of a .sup.13C and .sup.29Si-NMR spectroscopic analysis:

[0118] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2): δ=9.7 ppm (s, (Cl.sub.3Si).sub.3GeSiPh.sub.3),

[0119] −6.5 ppm (m, (Cl.sub.3Si).sub.3GeSiPh.sub.3).

[0120] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2): δ=137.1, 134.5, 131.7, 129.2 ppm.

EXAMPLE 7: PREPARATION OF NEOPENTATETRELANE (C), WHERE E-E′=GE AND R=PH

[0121] In a melt-sealed NMR tube, 0.081 g or 0.113 mmol corresponding to 1.0 eq of [nBu.sub.4N][(ClSi).sub.3Ge],

[0122] 0.015 g or 0.112 mmol corresponding to 1.0 eq of AlCl.sub.3 and

[0123] 0.038 g or 0.112 mmol corresponding to 1.0 eq of Ph.sub.3GeCl

[0124] were reacted in 0.7 ml of CD.sub.2Cl.sub.2 solvent, whereby a pale yellow solution was obtained.

[0125] The solvent was removed at atmospheric pressure.

[0126] By means of extraction with 3×4 ml of n-hexane and subsequent crystallization, neopentatetrelane (C) where E=E′=Ge and R=Ph was isolated in the form of pale yellow crystals.

[0127] The .sup.29Si-NMR spectrum of this example is shown in FIG. 7A. FIG. 7B shows the crystal structure of this neopentatetrelane.

[0128] Results of a .sup.1H, .sup.13C and .sup.29Si NMR spectroscopic analysis:

[0129] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2): δ=9.2 ppm (s, (Cl.sub.3Si).sub.3GeGePh.sub.3).

[0130] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2): δ=7.65-7.64 ppm (m, 2H),

[0131] 7.54-7.50 ppm (m, 1H), 7.49-7.46 ppm (m, 2H);

[0132] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2): δ=136.0, 133.1, 130.9, 129.4 ppm.