SILYLATED OLIGOGERMANES AND POLYCYCLIC SILICON-GERMANIUM COMPOUNDS, PROCESSES FOR THEIR PREPARATION AND THEIR USE FOR THE PREPARATION OF A SI- AND GE-CONTAINING SOLID

Abstract

The present invention relates to a compound of the formula (Ia) or the formula (Ib)

##STR00001##

a process for their preparation; and the use of the compound for the preparation of the Si- and Ge-containing solid.

Claims

1. A compound of the formula (Ia) or (Ib) ##STR00021## in which formula (Ia) n is an integer from 1 to 10; R.sup.1 and R.sup.2 are independently of each other selected from the group consisting of C.sub.1 to C.sub.20 alkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.2 to C.sub.20 alkynyl, C.sub.3 to C.sub.20 cycloalkyl, C.sub.6 to C.sub.20 aryl, C.sub.7 to C.sub.20 arylalkyl and C.sub.7 to C.sub.20 alkylaryl; and X.sup.1 is selected from the group consisting of H, SiH.sub.3, halogen and Si(Y.sup.1).sub.3 with Y.sup.1=halogen; ##STR00022## in which formula (Ib) E.sup.1 to E.sup.6 are independently of each other Si or Ge; X.sup.11 to X.sup.14 are independently of each other selected from the group consisting of H, SiH.sub.3, halogen and Si(Y.sup.2).sub.3; Y.sup.2 is independently selected from C.sub.1 to C.sub.20 alkyl and halogen; R.sup.3 to R.sup.14 are independently of each other selected from the group consisting of C.sub.1 to C.sub.20 alkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.2 to C.sub.20 alkynyl, C.sub.3 to C.sub.20 cycloalkyl, C.sub.6 to C.sub.20 aryl, C.sub.7 to C.sub.20 arylalkyl, C.sub.7 to C.sub.20 alkylaryl and Z; and Z is independently selected from the group consisting of H, halogen and C.sub.1 to C.sub.20 alkyl.

2. A compound according to claim 1, wherein n is an integer from 1 to 4.

3. A compound according to claim 1, wherein R.sup.1 and R.sup.2 are independently of each other selected from the group consisting of C.sub.1 to C.sub.20 alkyl and C.sub.6 to C.sub.20 aryl.

4. A compound according to claim 1, wherein R.sup.1 and R.sup.2 are independently of each other phenyl or methyl.

5. A compound according to claim 1, wherein R.sup.1 and R.sup.2 are the same.

6. A compound according to claim 1, wherein X1 is selected from the group consisting of H, SiH.sub.3, Cl and SiCl.sub.3.

7. A compound according to claim 1, wherein at least three of E.sup.1 to E.sup.6 are Ge and the remaining of E.sup.1 to E.sup.6 are Si.

8. A compound according to claim 1, wherein R.sup.3 to R.sup.14 are independently of each other selected from the group consisting of C.sub.1 to C.sub.20 alkyl and halogen.

9. A compound according to claim 1, wherein R.sup.3 to R.sup.14 are independently of each other selected from the group consisting of methyl and Cl.

10. A compound according to claim 1, wherein X.sup.11 to X.sup.14 are independently selected from the group consisting of H, SiH.sub.3, Si(C.sub.1 to C.sub.4 alkyl).sub.3, Cl and SiCl.sub.3.

11. A compound according to claim 1, wherein X.sup.11 to X.sup.14 are independently selected from the group consisting of SiCl.sub.3 and Si(CH.sub.3).sub.3.

12. Process for preparing a compound of the formula (Ia) according to claim 1 comprising reacting a compound of the formula (IIa) ##STR00023## with a compound of the formula (IIIa) ##STR00024## wherein X.sup.3 to X.sup.10 are independently of each other halogen; and R.sup.1 and R.sup.2 are as defined in one of the preceding claims; and hydrogenating the product obtained by reacting the compound of the formula (IIa) with the compound of the formula (IIIa).

13. The process according to claim 12, wherein the reaction of the compound of the formula (IIa) with the compound of the formula (IIIa) is carried out in the presence of a catalyst.

14. Process for preparing a compound of the formula (Ib) according to claim 1 comprising reacting a compound of the formula (IIb) ##STR00025## with a compound of the formula (IIIb) ##STR00026## wherein Hal.sup.1 to Hal.sup.8 are independently of each other halogen; and R.sup.3 and R.sup.4 are as defined in one of the preceding claims; and crystallizing the product of the reaction of the compounds (IIb) and (IIIb).

15. The process according to claim 14, wherein the reaction of the compound of the formula (IIb) with the compound of the formula (IIIb) is carried out in the presence of a catalyst.

16. The process according to claim 14, further comprising reacting the product obtained after the crystallization with a Grignard reagent.

17. Process for preparation of a Si- and Ge-containing solid, comprising heating the compound of the formula (Ia) or the compound of the formula (Ib) according to claim 1.

18. The process according to claim 17, wherein the preparation comprises heating the compound to a temperature of 300° C. or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0075] The invention will be described in detail below with reference to particularly preferred embodiments and exemplary embodiments. However, the invention is not limited to these particularly preferred embodiments and exemplary embodiments, wherein individual features of the particularly preferred embodiments and exemplary embodiments together with other features or features of the preceding general disclosure of the invention can serve to realize the invention.

[0076] FIG. 1 shows the crystal structure of the compound A7.

[0077] FIG. 2 shows the crystal structure of the compound A8.

[0078] The present invention relates to the novel silylated oligogermanes of the formula (Ia)

##STR00010##

[0079] The present invention also relates to the novel polycyclic silicon-germanium compounds of the formula (Ib)

##STR00011##

[0080] Compounds of the formula (Ia) are obtainable via a novel synthesis, for example starting from diorganyldichlorogermane and hexachlorodisilane. The target compounds (Ia) can be prepared, for example, by adding tetrabutylammonium chloride and subsequent hydration with lithium aluminum hydride. These oligogermanes are distinguished by their thermolysis behavior, for example, in the deposition of pure Si and Ge, the residue obtained here consisting of pure Si and Ge in the stoichiometric ratio.

[0081] Compounds of the formula (Ib) are obtainable via a novel synthesis, for example starting from diorganyldichlorogermane and hexachlorodisilane. The target compounds (Ib) can be prepared, for example, by adding tetrabutylammonium chloride and optionally subsequent reaction with a Grignard reagent. These polycyclic silicon-germanium compounds are distinguished by their thermolysis behavior, for example, in the deposition of pure Si and Ge, the residue obtained here consisting of pure Si and Ge in the stoichiometric ratio.

[0082] General Synthesis Route for the Compounds of the Formula (Ia)

[0083] The reaction of diorganodichlorogermanes with hexachlorodisilane with addition of tetrabutylammonium chloride followed by hydrogenation with LialH4 leads to the selective formation of the silylated oligogermanes H.sub.3Si—(GeR.sub.2).sub.n—X.sup.1 (where n=1-4; R=alkyl, aryl; X.sup.1═H, Cl, SiH.sub.3, SiCl.sub.3).

##STR00012##

[0084] Particularly preferred compounds which can be prepared in this way are the following compounds A1 to A8

##STR00013##

[0085] The compounds according to the invention can be prepared according to the following Scheme 1.

##STR00014##

[0086] Scheme 1 shows the reaction of diorganodichlorogermanes with hexachlorodisilane with addition of tetrabutylammonium chloride to give the trichlorosilylated oligogermanes Cl3Si—(GeR.sub.2).sub.n—Y (B, where n=1-4; R=alkyl, aryl; Y═Cl, SiCl.sub.3). The subsequent hydrogenation with LiAlH4 leads to the selective formation of the silylated oligogermanes H.sub.3Si—(GeR.sub.2).sub.n—Y (A, m it n=1-4; R=alkyl, aryl; Y═H, Cl, SiH.sub.3, SiCl.sub.3).

##STR00015##

[0087] Synthesis Examples for the Compounds of the Formula (Ia)

[0088] Synthesis of Cl.sub.3Si-Ph.sub.2Ge—SiCl.sub.3 (B1)

[0089] A solution of [nBu.sub.4N]Cl (90 mg, 0.34 mmol, 0.2 eq.), Ph.sub.2GeCl.sub.2 (500 mg, 1.70 mmol, 1 eq.), 5 ml of CH.sub.2Cl.sub.2 and Si.sub.2Cl.sub.6 (1800 mg, 6.80 mmol, 4 eq.) was stirred at room temperature overnight and then freed from all volatile constituents under reduced pressure. The orange-colored viscous residue was extracted with 6 ml of n-hexane and all volatile constituents were removed from the filtrate under reduced pressure. In this way, Cl.sub.3Si-Ph.sub.2Ge—SiCl.sub.3 (79%, 659 mg, 1.34 mmol) was obtained as a colorless, viscous liquid.

[0090] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=7.57-7.52 (m, 4H), 7.44-7.35 ppm (m, 6H).

[0091] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=136.0 (ortho), 131.1 (para), 129.9 (meta), 129.4 ppm (ipso).

[0092] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=9.7 ppm.

[0093] EA (%): Calculated for C.sub.12H.sub.10Si.sub.2Cl.sub.6Ge [495.70 g/mol]: C 29.08, H 2.03; found: C 29.51, H 2.07.

[0094] Synthesis of Cl.sub.3Si-Me.sub.2Ge—SiCl.sub.3 (B2)

[0095] [nBu.sub.4N]Cl (200 mg, 0.73 mmol, 0.2 eq.), Me.sub.2GeCl.sub.2 (500 mg, 3.63 mmol, 1 eq.), 10 ml of CH.sub.2Cl.sub.2 and Si.sub.2Cl.sub.6 (1950 mg, 7.26 mmol, 2 eq.) were stirred at room temperature for 3 hours and then all volatile constituents were removed under reduced pressure. The crude product was extracted twice with 5 ml of n-hexane each time and all volatile constituents were removed from the filtrate under reduced pressure. In this way, 370 mg of a colorless liquid were obtained. NMR spectroscopy and GC/MS confirmed the presence of a mixture of Cl.sub.3Si-Me.sub.2Ge—SiCl.sub.3 and Cl.sub.3Si-Me.sub.2Ge-Me.sub.2Ge—SiCl.sub.3.

[0096] Cl.sub.3Si-Me.sub.2Ge—SiCl.sub.3 was identified using the following signals:

[0097] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=0.79 ppm (s, 6H).

[0098] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=−5.2 ppm.

[0099] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=13.2 ppm.

[0100] Synthesis of Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3 (B3)

[0101] [nBu.sub.4N]Cl (180 mg, 0.65 mmol, 0.2 eq.), Ph.sub.2GeCl.sub.2 (900 mg, 3.02 mmol, 1 eq.), 10 ml of CH.sub.2Cl.sub.2 and Si.sub.2Cl.sub.6 (1600 mg, 5.95 mmol, 2 eq.) were stirred at room temperature for 3 hours and then all volatile constituents were removed under reduced pressure. The crude product was washed dropwise with a total of 2.5 ml of CH.sub.2Cl.sub.2 in order to obtain Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3 as a colorless solid in 88% yield (956 mg, 1.32 mmol).

[0102] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=7.62-7.56 (m, 8H), 7.54-7.38 ppm (m, 12H).

[0103] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=136.3 (ortho), 132.2 (ipso), 130.5 (para), 129.4 ppm (meta).

[0104] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=12.4 ppm.

[0105] EA (%): Calculated for C.sub.24H.sub.20Si.sub.2Cl.sub.6Ge.sub.2 [722.55 g/mol]: C 39.90, H 2.79; found: C 40.64, H 3.02.

[0106] Synthesis of Cl.sub.3Si-Me.sub.2Ge-Me.sub.2Ge—SiCl.sub.3 (B4)

[0107] [nBu4N]Cl (800 mg, 2.91 mmol, 0.4 eq.), Me.sub.2GeCl.sub.2 (1000 mg, 7.27 mmol, 1 eq.), 20 ml of CH.sub.2Cl.sub.2 and Si.sub.2Cl.sub.6 (3900 mg, 14.54 mmol, 2 eq.) were stirred at room temperature for 24 hours and then all volatile constituents were removed under reduced pressure. The crude product was extracted four times with 5 ml of n-hexane each time and all volatile constituents were removed from the filtrate under reduced pressure. In this way, Cl.sub.3Si-Me.sub.2Ge-Me.sub.2Ge—SiCl.sub.3 (34%, 589 mg, 1.24 mmol) was obtained as a colorless liquid.

[0108] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=0.72 ppm (s, 12H).

[0109] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=−4.3 ppm.

[0110] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=16.7 ppm.

[0111] Synthesis of Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—Cl (B5)

[0112] [nBu.sub.4N]Cl (10 mg, 0.03 mmol, 0.1 eq.), Ph.sub.2GeCl.sub.2 (100 mg, 0.34 mmol, 1 eq.), 1 ml of CD.sub.2Cl.sub.2 and Si.sub.2Cl.sub.6 (90 mg, 0.34 mmol, 1 eq.) were mixed in a glass and then half the batch was added to an NMR tube. After melting in oil pump vacuum, Cl-Ph.sub.2Ge-Ph.sub.2Ge—Cl, Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl and Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3 were detected in the reaction solution by means of NMR spectroscopy.

[0113] Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—Cl was identified using the following signals:

[0114] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=7.80-7.00 (m, 20H).

[0115] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—Cl: δ=136.6 (ipso), 136.1 (ortho), 134.1 (ortho), 131.8 (ipso), 131.0 (para), 130.6 (para), 129.5 (meta), 129.2 ppm (meta).

[0116] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=12.1 ppm.

[0117] Synthesis of H.sub.3Si-Ph.sub.2Ge—H (A1)

[0118] The product from the synthesis of H.sub.3Si-Ph.sub.2Ge—SiH.sub.3 was stored at room temperature for 6 months. The subsequent investigation by means of NMR spectroscopy and GC/MS confirmed the formation of H.sub.3Si-Ph.sub.2Ge—H.

[0119] H.sub.3Si-Ph.sub.2Ge—H was identified using the following signals:

[0120] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=7.70-7.20 (m), 5.07 (Ge—H, q, J=3.2 Hz, 1H), 3.57 ppm (SiH3, d, J=3.2 Hz, 3H).

[0121] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=136.1 (ipso), 135.5 (ortho), 129.3 (para), 128.9 ppm (meta).

[0122] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=−94.9 ppm (qd, .sup.1J.sub.HSI=199.7 Hz, .sup.2J.sub.HSI=13.3 Hz).

[0123] Synthesis of H.sub.3Si-Ph.sub.2Ge—SiH.sub.3 (A2)

[0124] Cl.sub.3Si-Ph.sub.2Ge—SiCl.sub.3 (400 mg, 0.807 mmol, 1 eq.) was dissolved in 10 ml of Et.sub.2O and LiAlH.sub.4 (93 mg, 2.42 mmol, 3 eq.) was added in portions. The solution remained clear and colorless and a gray solid precipitated. After stirring for 30 minutes, all volatile constituents were removed under reduced pressure and the residue was stirred with 8 ml of n-hexane for 16 hours. Filtration of the n-hexane solution and liberation of the extract from all volatile constituents under reduced pressure yielded H.sub.3Si-Ph.sub.2Ge—SiH.sub.3 (55%, 128 mg, 0.443 mmol) as a viscous, colorless liquid. The product was identified by means of NMR spectroscopy and GC/MS.

[0125] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=7.42-7.38 (m, 4H), 7.27-7.23 (m, 6H), 3.50 ppm (s, 6H).

[0126] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=136.8 (ipso), 135.4 (ortho), 129.1 (para), 128.9 ppm (meta).

[0127] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=−91.2 ppm (qq, .sup.1J.sub.HSI=200 Hz, .sup.3J.sub.HSI=3 Hz).

[0128] Synthesis of H.sub.3Si-Me.sub.2Ge—SiH.sub.3 (A3) and H.sub.3Si-Me.sub.2Ge-Me.sub.2Ge—SiH.sub.3 (A5)

[0129] 50 mg of a mixture of Cl.sub.3Si-Me.sub.2Ge—SiCl.sub.3 (B2) and Cl.sub.3Si-Me.sub.2Ge-Me.sub.2Ge—SiCl.sub.3 (B4) was dissolved in 0.8 ml of Et.sub.2O in an NMR tube and an excess of LiAlH.sub.4 (15 mg, 0.4 mmol, about 3 eq.) was slowly added. 0.2 ml of the solution was taken for a GC/MS sample and diluted with a further 0.5 ml of Et.sub.2O. The remaining reaction solution was melted in the NMR tube under vacuum and measured by NMR spectroscopy. GC/MS and NMR spectroscopy confirmed the formation of H.sub.3Si-Me.sub.2Ge—SiH.sub.3 and H.sub.3Si-Me.sub.2Ge-Me.sub.2Ge—SiH.sub.3.

[0130] .sup.1H NMR (500.2 MHz, Et.sub.2O, 298 K): δ=0.93 ppm; H.sub.3Si-Me.sub.2Ge-Me.sub.2Ge-SiH.sub.3: δ=0.89 ppm.

[0131] .sup.13C{.sup.1H} NMR (125.8 MHz, Et.sub.2O, 298 K): δ=−4.0 ppm; H.sub.3Si-Me.sub.2Ge-Me.sub.2Ge-SiH.sub.3: δ=−4.8 ppm.

[0132] .sup.29Si NMR (99.4 MHz, Et.sub.2O, 298 K): δ=−90.8 ppm (qm, .sup.1J.sub.HSI=196 Hz); H.sub.3Si-Me.sub.2Ge-Me.sub.2Ge-SiH.sub.3: δ=−94.7 ppm (qm, .sup.1J.sub.HSI=191 Hz).

[0133] Synthesis of H.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiH.sub.3 (A4)

[0134] Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3 (200 mg, 0.280 mmol, 1 eq.) was dissolved in 6 ml of Et.sub.2O and LiAlH.sub.4 (37 mg, 0.98 mmol, 3.5 eq.) was added in portions. The solution remained clear and colorless and a gray solid precipitated. After stirring for 30 minutes, all volatile constituents were removed under reduced pressure and the residue was stirred with 8 ml of n-hexane for 16 hours. Filtration of the n-hexane solution and liberation of the extract from all volatile constituents under reduced pressure yielded H.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiH.sub.3 (55%, 128 mg, 0.44 mmol) as a colorless, crystalline solid. The product was identified by means of NMR spectroscopy.

[0135] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=7.44-7.39 (m, 8H), 7.38-7.27 (m, 13H), 3.60 ppm (s, 6H).

[0136] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=127.1 (ipso), 135.8 (ortho), 129.1 (para), 128.8 ppm (meta).

[0137] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=−92.6 ppm (q, .sup.1J.sub.HSI=199.6 Hz).

[0138] Synthesis of H.sub.3Si-Ph.sub.2Ge—SiCl.sub.3 (A6)

[0139] Cl.sub.3Si-Ph.sub.2Ge—SiCl.sub.3 (50 mg, 0.10 mmol, 1 eq.) in 0.5 ml of Et.sub.2O was initially charged in an NMR tube and LiAlH.sub.4 (6 mg, 0.14 mmol, 1.4 eq.) was added. A gray solid precipitated from the colorless reaction solution. .sup.13C and .sup.29Si NMR spectroscopy showed Cl.sub.3Si-Ph.sub.2Ge—SiCl.sub.3, H.sub.3Si-Ph.sub.2Ge—SiCl.sub.3 and H.sub.3Si-Ph.sub.2Ge—SiH.sub.3 as reaction products.

[0140] NMR signals of H.sub.3Si-Ph.sub.2Ge—SiCl.sub.3:

[0141] .sup.13C{.sup.1H} NMR (125.8 MHz, Et.sub.2O, 298 K): δ=135.7 (ortho), 132.6 (ipso), 130.4 (para), 129.7 ppm (meta).

[0142] .sup.29Si NMR (99.4 MHz, Et.sub.2O, 298 K): δ=15.7, −93.4 ppm (q, .sup.1J.sub.HSI=207 Hz).

[0143] Synthesis of H.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3 (A7)

[0144] Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3 (200 mg, 0.280 mmol, 1 eq.) in 2 ml of Et.sub.2O was initially charged and LiAlH.sub.4 (10 mg, 0.28 mmol, 1 eq.) was slowly added. The solution remained colorless and a gray solid precipitated. The solid was filtered off and the filtrate was freed from the solvent under ambient pressure. The residue was extracted with 4 ml of n-hexane and then all volatile constituents of the extract were removed under ambient pressure. .sup.13C and .sup.29Si NMR spectroscopy of the solid obtained confirmed the presence of the starting material Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3, H.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3 and H.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiH.sub.3. It was also possible to obtain the crystal structure of H.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3 by means of X-ray diffractometry.

[0145] NMR signals of H.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3:

[0146] .sup.13C{1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=136.2 (ortho), 136.0 (ortho), 135.5 (ipso), 133.6 (ipso), 130.1 (para), 129.6 (para), 129.3 (meta), 129.0 ppm (meta).

[0147] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=−90.7 ppm (q, .sup.1J.sub.HSI=204 Hz).

[0148] Synthesis of H.sub.3Si—(Ph.sub.2Ge).sub.4—SiH.sub.3 (A8)

[0149] An NMR tube was filled with [nBu.sub.4N]Cl (10 mg, 0.03 mmol, 0.2 eq.), Ph.sub.2GeCl.sub.2 (50 mg, 0.17 mmol, 1 eq.), 0.5 ml of CD.sub.2Cl.sub.2 and Si.sub.2Cl.sub.6 (90 mg, 0.34 mmol, 2 eq.). .sup.13C and .sup.29Si NMR spectroscopy of the clear, colorless solution confirmed the presence of Cl.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiCl.sub.3, Cl.sub.3Si-Ph.sub.2Ge—SiCl.sub.3 and SiCl.sub.4. The NMR tube was opened and all volatile constituents were removed under ambient pressure. The residue was dissolved in a new NMR tube in 0.5 ml of Et.sub.2O and LiAlH.sub.4 (7 mg, 0.17 mmol, 1 eq.) was added. A colorless solution with a gray sediment and a fine, colorless solid was then present. .sup.13C and .sup.29Si NMR spectroscopy of the reaction solution gave the signals of several unknown species which could not be characterized more precisely. After opening the NMR tube and removing the volatile constituents under ambient pressure, a crystal was obtained which was identified by means of X-ray diffractometry as the tetragerman H.sub.3Si—(Ph.sub.2Ge).sub.4—SiH.sub.3.

[0150] Synthesis Examples for the Compounds of the Formula (Ib)

[0151] Synthesis of C.sub.10H.sub.30Cl.sub.4Ge.sub.5Si.sub.9 (C1)

##STR00016##

[0152] [nBu.sub.4N]Cl (161 mg, 0.58 mmol, 0.2 eq.), Me.sub.2GeCl.sub.2 (500 mg, 2.88 mmol, 1 eq.), 10 ml of CH.sub.2Cl.sub.2 and Si.sub.2Cl.sub.6 (3092 mg, 11.5 mmol, 4 eq.) were stirred at room temperature for 3 hours and then all volatile constituents were removed under reduced pressure. The crude product was washed twice with 5 ml of n-hexane each time and the residue was dissolved in CH.sub.2Cl.sub.2. A colourless solid crystallized out over time. Washing with CH.sub.2Cl.sub.2 yielded C1 (4%, 32 mg, 0.025 mmol) as a colorless crystalline solid. The product was characterized by means of X-ray diffractometry (orthorhombic, Cmc2.sub.1) and NMR spectroscopy.

[0153] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=1.00, 0.94, 0.93 ppm.

[0154] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=2.57, 2.23, 1.97 ppm.

[0155] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=16.2, 12.1, −80.7, −83.3 ppm.

[0156] Synthesis of C.sub.8H.sub.24Cl.sub.16Ge.sub.4Si.sub.10 (C2)

##STR00017##

[0157] [nBu.sub.4N]Cl (161 mg, 0.58 mmol, 0.2 eq.), Me.sub.2GeCl.sub.2 (500 mg, 2.88 mmol, 1 eq.), 10 ml of CH.sub.2Cl.sub.2 and Si.sub.2Cl.sub.6 (3092 mg, 11.5 mmol, 4 eq.) were filled into a bulkhead bottle. After a few days, colorless crystals had formed which could be isolated by means of filtration. Washing with CH.sub.2Cl.sub.2 yielded C2 (18%, 163 mg, 0.13 mmol) as a colorless crystalline solid. The product was characterized by means of X-ray diffractometry (trigonal, R-3) and NMR spectroscopy.

[0158] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=1.03 ppm.

[0159] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=1.59 ppm.

[0160] .sup.29Si NMR (99.4 MHZ, CD.sub.2Cl.sub.2, 298 K): δ=11.9, −80.8 ppm.

[0161] Synthesis of C.sub.22H.sub.66Cl.sub.2Ge.sub.5Si.sub.9 (C3)

##STR00018##

[0162] C1 (12 mg, 0.009 mmol, 1 eq.) and 0.5 ml of Et.sub.2O were filled into an NMR tube and an Et.sub.2O solution of MeMgBr (3 M, 0.1 ml, 0.30 mmol, 30 eq.) was added with ice cooling. The NMR tube was melted in under vacuum. After about two weeks at room temperature, a complete conversion could be observed by means of NMR spectroscopy. The NMR tube was then opened, the contents were transferred together with 3 ml of Et.sub.2O into a Schlenk flask and then 0.05 ml of MeOH was added with ice cooling. After stirring for 10 minutes, all volatile constituents were removed, and the residue was extracted with a total of 7 ml of n-hexane. Again, all volatile constituents were removed from the extract, whereupon C3 (82%, 8 mg, 0.008 mmol) was obtained as a colorless crystalline solid. The product was characterized by means of X-ray diffractometry (orthorhombic, Cmcm) and NMR spectroscopy.

[0163] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=0.66, 0.61, 0.59, 0.35, 0.27 ppm.

[0164] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=4.06, 3.81, 3.60, 3.27, 2.92 ppm.

[0165] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=2.6, 3.5, 91.5, 97.2 ppm.

[0166] Synthesis of C.sub.20H.sub.60Cl.sub.4Ge.sub.4Si.sub.10 (C4)

##STR00019##

[0167] C2 (20 mg, 0.015 mmol, 1 eq.) and 0.5 ml of Et.sub.2O were filled into an NMR tube and an Et.sub.2O solution of MeMgBr (3 M, 0.2 ml, 0.60 mmol, 40 eq.) was added with ice cooling. The NMR tube was melted in under vacuum. After heating for 14 h at 60° C., a complete conversion could be observed by means of NMR spectroscopy. The further purification was then carried out analogously to C3.

[0168] Finally, C4 (89%, 16 mg, 0.016 mmol) was obtained as a colorless crystalline solid. The product was characterized by means of X-ray diffractometry (orthorhombic, Pbca) and NMR spectroscopy.

[0169] .sup.1H NMR (500.2 MHz, CD.sub.2Cl.sub.2, 298 K): δ=0.70, 0.37 ppm.

[0170] .sup.13C{.sup.1H} NMR (125.8 MHz, CD.sub.2Cl.sub.2, 298 K): δ=3.7, 2.5 ppm.

[0171] .sup.29Si NMR (99.4 MHz, CD.sub.2Cl.sub.2, 298 K): δ=−1.8, −91.6 ppm.

[0172] Preparation of Si- and Ge-Containing Solids

[0173] Si- and Ge-Containing Solids can be prepared starting from the compounds according to the invention, for example according to the following reaction scheme.

##STR00020##

[0174] Deposition of SiGe at 600° C.

[0175] H.sub.3Si-Ph.sub.2Ge-Ph.sub.2Ge—SiH.sub.3 (13 mg, 0.025 mmol) was weighed into a crucible and a thermogravimetric analysis (TGA) was carried out. For this purpose, the mixture was heated to 600° C. under an argon atmosphere at a rate of 10 K/min, this temperature was maintained for 5 minutes and the sample was then cooled again to room temperature at the same rate. The residue obtained, a brownish powder, was examined by means of EDX. For this purpose, some of the sample was applied to a support and coated with gold for better measurement accuracy. In addition to silicon and germanium, the subsequent measurement showed only gold, as well as small amounts of carbon, oxygen and aluminum. The evaluation of the data of two analyzed regions showed a silicon-germanium ratio of 1.0:1.0 or 1.0:1.1.

[0176] The features of the invention disclosed in the above description and in the claims can be essential both individually and in any combination for the realization of the invention in its various embodiments.