10038-98-9

Basic information

• Product Name: Germanium chloride
• Synonyms: GERMANIUM(IV) CHLORIDE;GeCl4;Germane, tetrachloro-;Germane,tetrachloro-;Germanium chloride (GeCl4);Germanium, tetrachloro-;tetrachloro-german;Tetrachlorogermane
• CAS NO: 10038-98-9
• Molecular Formula: Cl₄Ge
• Molecular Weight: 214.45
• EINECS: 233-116-7
• Product Categories: Inorganics;metal halide;Catalysis and Inorganic Chemistry;Chemical Synthesis;Germanium;Germanium Salts;Materials Science;Metal and Ceramic Science;Salts;Ge;Ultra-High Purity Materials
• Mol File: 10038-98-9.mol
• Article Data: 17

Chemical Properties

• Melting Point: -49.5 °C
• Boiling Point: 83 °C(lit.)
• Flash Point: 83.1°C
• Appearance: Colorless/Liquid
• Density: 1.844 g/mL at 25 °C
• Vapor Pressure: 76 mm Hg ( 20 °C)
• Refractive Index: 1.4644
• Storage Temp.: Store below +30°C.
• Solubility: Soluble in ether, benzene, chloroform, carbon tetrachloride. Ins
• Water Solubility: DECOMPOSES
• Sensitive: Moisture Sensitive
• Merck: 14,4410
• CAS DataBase Reference: Germanium chloride(CAS DataBase Reference)
• NIST Chemistry Reference: Germanium chloride(10038-98-9)
• EPA Substance Registry System: Germanium chloride(10038-98-9)

Safety Data

• Hazard Codes: C
• Statements: 14-34-67-40-37
• Safety Statements: 26-27-36-45-8-36/37/39-25
• RIDADR: UN 3390 6.1/PG 1
• WGK Germany: 3
• RTECS: LY5225000
• F: 10-19
• TSCA: Yes
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 10038-98-9(Hazardous Substances Data)

Usage

Uses

1. Used in Chemical Synthesis:
Germanium chloride is used as a catalyst in the conversion of carbohydrates into 5-hydroxymethylfurfural in ionic liquids. It is also used as a reducing agent in combination with triphenylphosphine (TPP) for the reduction of alpha-bromo carboxylic acid derivatives.
2. Used in Semiconductor Industry:
Germanium chloride is employed in the production of pure germanium, which is an essential material in the semiconductor industry.
3. Used in Optical Fibers:
Germanium chloride is one of the most important dopants in silica glass for optical fibers, enhancing their optical properties.
4. Used in Optics and Photography:
Germanium chloride is used in the preparation of germanium dioxide, which is utilized in wide camera lenses, microscopy, and IR-transparent glasses/windows/lenses.
5. Used in Fiber-Optic Technology:
Germanium dioxide, derived from germanium chloride, is used for the core of fiber-optic lines, improving their performance in data transmission.
6. Used in Microwave Preparation:
Germanium(IV) chloride is used in the microwave preparation of Ge2Cl6, a colorless crystalline material that has been further studied for its low-valent germanium compounds.
7. Used in the Preparation of Germanium Compounds:
Germanium(IV) chloride is a key compound in the preparation of various germanium compounds, which have diverse applications in different industries.

Preparation

Germanium(IV) chloride is prepared by reacting germanium metal with chlorine; or by treating germanium oxide, GeO2, with hydrochloric acid: Ge + 2Cl2 → GeCl4 GeO2 + 4HCl → GeCl4 + 2H2O Germanium(IV) chloride often is obtained as a byproduct of germanium metal production. The process involves heating germanium oxide, GeO2, with sodium chloride and coal. The vapors of germanium(IV) chloride and other volatile chlorides formed from the impurity metals are condensed. The product is isolated by fractional distillation. Further purification may be achieved by fractional distillation in 8N HCl and chlorine, or in the presence of other oxidizing agents in quartz stills. Germanium(IV) chloride also is obtained by chlorination of germanium(II) chloride at ambient temperature. The reaction is rapid. GeCl2 + Cl2 → GeCl4

Reactions

Germanium(IV) chloride reacts with water, hydrolyzing to germanium oxide and hydrochloric acid: GeCl4 + 2H2O → GeO2 + 4HCl The rate of hydrolysis is slower than the corresponding silicon analog, with hydrolysis occurring only partially. When heated with hydrogen at 1,000°C in a quartz reactor, it is converted into germanium(I) chloride, condensing onto the wall of the reactor: 2GeCl4 + 3H2→ 2GeCl + 6HCl When vapors of GeCl4 are passed over germanium at elevated temperatures, the product is germanium(II) chloride, GeCl2: GeCl4 + Ge→ 2GeCl2 Reaction with lithium aluminum hydride in ether forms monogermane, GeH4: GeCl4 + LiAlH4 →GeH4 + LiCl + AlCl3 Reactions with antimony trifluoride, SbF3 in the presence of antimony pentachloride, SbCl5, form mixed halides of compositions: GeCl3F, GeCl3F2, GeCl2F2, and GeClF3. Reactions with alcohols in the presence of an amine yield alkoxides: GeCl4 + 4CH3OH + 4C2H5NH2 → Ge(OCH3)4 + 4C2H5N?HCl Germanium forms six coordinate adducts, such as GeCl4(L)2 with many neutral ligands.

Hazard

Toxic material

Flammability and Explosibility

Nonflammable

Safety Profile

Poison by intravenous route. Mddly toxic by inhalation. A skin, severe eye, and mucous membrane irritant. Will react violently with water or steam to produce toxic and corrosive fumes. When heated to decomposition it emits toxic fumes of Cl-. See also GERMANIUM COMPOUNDS.

Purification Methods

Traces of Cl2 and HCl can be removed from the liquid by blowing dry air through it for a few hours at room temperature or by shaking it with Hg or Hg2Cl2 and then fractionating it in a vacuum. It decomposes on heating at 950o. It has a sharp penetrating odour and fumes in moist air to give a chalky coat of GeO2. It is slowly hydrolysed by H2O to give GeO2, but distils from conc HCl. [Foster et al. Inorg Synth II 109 1946, Dennis & Hance J Am Chem Soc 44 304 1922, Schenk in Handbook of Preparative Inorganic Chemistry (Ed. Brauer) Academic Press Vol I p 715 1963.] LACHRYMATORY. Glass powder (100-300 mesh). Washed with 10% HNO3, water and dry in air.

InChI:InChI=1/4ClH.Ge/h4*1H;/q;;;;+4/p-4

Synthetic route

germanium (7440-56-4) → germaniumtetrachloride (10038-98-9)

Conditions	Yield
In melt Electrolysis; electrolysis in AlCl3-NaCl-KCl, NaCl-KCl, NaCl-PbCl2, LiCl-KCl, or NaCl-AlCl3 melts;; condensation of the anodic gas; purity 99.9%;	100%
With chloroform In neat (no solvent) react. of evaporated Ge vapor with CHCl3 (at 50°C for 3 h); GLC;	0.5%
With chlorine In neat (no solvent) Ge in small pieces was chlorinated at 460°C; purified by column distn. at 83°C;

germanium(II) chloride dioxane + triphenylantimony dichloride (594-31-0, 34716-91-1, 20265-29-6) → triphenylantimony (603-36-1) + germaniumtetrachloride (10038-98-9)

Conditions	Yield
In toluene byproducts: dioxane; standing (room temperature, 24 h); liquid chromy.;	A 93% B 91%

((C6H5)3P)2Ni(HgGe(C6H5)3)Ge(C6H5)3 → (P(C6H5)3)2NiCl2*HgCl2 + triphenylgermane (2816-43-5) + germaniumtetrachloride (10038-98-9)

Conditions	Yield
With hydrogenchloride In toluene byproducts: H2; mixt. keeping for 1 d at room temp. in argon atmosphere or in evac. sealed ampul; ppt. washing; elem. anal., GLC anal., mass spoectroscopy;	A 92% B 51% C n/a

((C6H5)3P)2Ni(CdGe(C6H5)3)Ge(C6H5)3 → (P(C6H5)3)2NiCl2*CdCl2*4HCl + triphenylgermane (2816-43-5) + germaniumtetrachloride (10038-98-9)

Conditions	Yield
With hydrogenchloride In toluene byproducts: H2; mixt. keeping for 1 d at room temp. in argon atmosphere or in evac. sealed ampul; ppt. washing; elem. anal., GLC anal., mass spoectroscopy;	A 87% B 45% C n/a

Ge(NCO)4 + Dichlorophenylphosphine (644-97-3) → germaniumtetrachloride (10038-98-9)

Conditions	Yield
treating Ge(NCO)4 with C6H5PCl2;;	78%
treating Ge(NCO)4 with C6H5PCl2;;	78%

germanium(IV) isocyanate (4756-66-5) + Dichlorophenylphosphine (644-97-3) → germaniumtetrachloride (10038-98-9)

Conditions	Yield
In neat (no solvent) distillation with C6H5PCl2;;	78%
In neat (no solvent) distillation with C6H5PCl2;;	78%

aluminium trichloride (7446-70-0) + germanium tetrafluoride (7783-58-6) → germaniumtetrachloride (10038-98-9)

Conditions	Yield
In neat (no solvent) reaction of gaseous GeF4 with H2O-free AlCl3 in special app. at 210 °C (1 atm);;	78%
In neat (no solvent) reaction of gaseous GeF4 with H2O-free AlCl3 in special app. at 210 °C (1 atm);;	78%
In neat (no solvent) reaction of gaseous GeF4 with H2O-free AlCl3 in special app. at 200 °C (1 atm);;	43%
In neat (no solvent) reaction of gaseous GeF4 with H2O-free AlCl3 in special app. at 200 °C (1 atm);;	43%

((C6H5)3P)2Pt(HgGe(C6H5)3)Ge(C6H5)3 → (P(C6H5)3)2PtCl2(Ge(C6H5)3)(H) (83347-99-3) + triphenylgermane (2816-43-5) + germaniumtetrachloride (10038-98-9) + mercury dichloride

Conditions	Yield
With hydrogenchloride In toluene byproducts: H2; mixt. keeping for 1 d at room temp. in argon atmosphere or in evac. sealed ampul; ppt. washing, HgCl2 recrystn. (ethanol); elem. anal., GLC anal., mass spoectroscopy;	A 77% B 40% C n/a D 73%

germanium tetrabromide (13450-92-5) + Dichlorophenylphosphine (644-97-3) → germaniumtetrachloride (10038-98-9)

Conditions	Yield
In neat (no solvent) byproducts: GeCl3Br; distillation of GeBr4 with C6H5PCl2;; product contg. GeCl3Br;;	57%

tetrachloromethane (56-23-5) + germanium (7440-56-4) → germaniumtetrachloride (10038-98-9) + trichloro(trichloromethyl)germane (25105-16-2)

Conditions	Yield
reaction of germanium atoms with organic halide by co-condensation under vac. at 77 K; GC-MASS;	A 50% B 7%
In neat (no solvent) react. of evaporated Ge vapor with CCl4 (at 50°C for 3 h); GLC;	A 1% B 16%
With copper In gas vaporization of Ge and Cu (alumina-coated tungsten crucible, 1200-1300°C, 5E-3 Torr), introduction into reaction flask (cooled with liq. N2 during Ge vaporization) together with vapor of organic halide, warming to room temp., standing for 1.5 h; GC-MS, GLC;	A <10 B 12%

germanium tetrafluoride (7783-58-6) + magnesium chloride (7786-30-3) → germaniumtetrachloride (10038-98-9)

Conditions	Yield
In neat (no solvent) reaction of gaseous GeF4 with H2O-free MgCl2 in special app. at 610 °C (1 atm);;	45%
In neat (no solvent) reaction of gaseous GeF4 with H2O-free MgCl2 in special app. at 610 °C (1 atm);;	45%

iron(III) chloride (7705-08-0) + germanium tetrafluoride (7783-58-6) → germaniumtetrachloride (10038-98-9)

Conditions	Yield
In neat (no solvent) reaction of gaseous GeF4 with H2O-free FeCl3 in special app. at 350 °C (1 atm);;	40%
In neat (no solvent) reaction of gaseous GeF4 with H2O-free FeCl3 in special app. at 350 °C (1 atm);;	40%

trichlorophenylgermane (1074-29-9) + 3-chloroprop-1-ene (107-05-1) → germaniumtetrachloride (10038-98-9) + allyl(trichloro)germane (762-67-4)

Conditions	Yield
In neat (no solvent) byproducts: benzene, chlorobenzene; passing through tubular quartz reactor (contact time 30 s, temperature 500°C; yield 9.8 and 11.3% at 550°C depending on the reactant ratio); products condensing;	A n/a B 37.1%

Methyltrichlorosilane (75-79-6) + dimethyldiphenylgermane (7301-42-0) → germaniumtetrachloride (10038-98-9) + phenyldimethylchlorogermane (22702-76-7) + methylphenylgermanium dichloride (25179-00-4) + trichlorophenylgermane (1074-29-9)

Conditions	Yield
aluminium trichloride In solid Si-compound reacted with (CH3)2Ge(C6H5)2 at 110-120°C for 3 h in presence of AlCl3;	A 35.9% B 5.1% C 4.1% D 6.7%

Methyltrichlorosilane (75-79-6) + dimethyldiphenylgermane (7301-42-0) → chlorotriphenylgermane (1626-24-0) + germaniumtetrachloride (10038-98-9) + phenyldimethylchlorogermane (22702-76-7) + trichlorophenylgermane (1074-29-9)

Conditions	Yield
aluminium trichloride In solid Si-compound reacted with (CH3)2Ge(C6H5)2 at 110-120°C for 3 h in presence of AlCl3;	A 2.3% B 35.5% C 10.3% D 2.7%

N-[(trichlorogermyl)methyl]phthalimide (95601-29-9) → Cl3GeCH2NH2*HCl + germaniumtetrachloride (10038-98-9) + benzene-1,2-dicarboxylic acid (88-99-3)

Conditions	Yield
With hydrogenchloride In hydrogenchloride refluxed for 7 h; ppt. separated and dried, GeCl4 distd. off, residue shaken with CHCl3, phthalic acid filtered off;	A 0% B n/a C 35%

chloro-trimethyl-silane (75-77-4) + dimethyldiphenylgermane (7301-42-0) → germaniumtetrachloride (10038-98-9) + methylphenylgermanium dichloride (25179-00-4)

Conditions	Yield
aluminium trichloride In solid Si-compound reacted with (CH3)2Ge(C6H5)2 at 110-120°C for 3 h in presence of AlCl3;	A 9.4% B 29.7%

chloro-trimethyl-silane (75-77-4) + dimethyldiphenylgermane (7301-42-0) → germaniumtetrachloride (10038-98-9) + phenyldimethylchlorogermane (22702-76-7) + methylphenylgermanium dichloride (25179-00-4)

Conditions	Yield
aluminium trichloride In solid Si-compound reacted with (CH3)2Ge(C6H5)2 at 110-120°C for 3 h in presence of AlCl3;	A 11.2% B 3.5% C 22.8%
aluminium trichloride In solid Si-compound reacted with (CH3)2Ge(C6H5)2 at 110-120°C for 3 h in presence of AlCl3;	A 8.4% B 4.6% C 16.4%

tetrachlorosilane (10026-04-7, 53609-55-5) + dimethyldiphenylgermane (7301-42-0) → germaniumtetrachloride (10038-98-9) + phenyldimethylchlorogermane (22702-76-7) + methylphenylgermanium dichloride (25179-00-4) + trichlorophenylgermane (1074-29-9)

Conditions	Yield
aluminium trichloride In solid Si-compound reacted with (CH3)2Ge(C6H5)2 at 110-120°C for 3 h in presence of AlCl3;	A 21.6% B 0.4% C 2.2% D 11%

germanium (7440-56-4) + chloroform (67-66-3) → germaniumtetrachloride (10038-98-9) + Dichlormethyltrichlorgerman (21572-22-5)

Conditions	Yield
reaction of germanium atoms with organic halide by co-condensation under vac. at 77 K; GC-MASS;	A 15% B 8%
In gas vaporization of Ge (alumina-coated tungsten crucible, 1200-1300°C, 5E-3 Torr), introduction into reaction flask (cooled with liq. N2 during Ge vaporization) together with vapor of org. halide, warming to room temp., standing for 1.5 h; GC-MS, GLC;	A 15% B 8%

trichlorophenylgermane (1074-29-9) + isoprene (78-79-5) → germaniumtetrachloride (10038-98-9) + isopentyltrichlorogermane + 3-methyl-3-buten-2-yl germanium trichloride (266323-41-5)

Conditions	Yield
In neat (no solvent) byproducts: benzene, chlorobenzene; passing through tubular quartz reactor (630°C, contact time 30 s); products condensing;	A n/a B 13% C 5.9%

tetrachlorosilane (10026-04-7, 53609-55-5) + dimethyldiphenylgermane (7301-42-0) → germaniumtetrachloride (10038-98-9) + methylphenylgermanium dichloride (25179-00-4)

Conditions	Yield
aluminium trichloride In solid Si-compound reacted with (CH3)2Ge(C6H5)2 at 110-120°C for 3 h in presence of AlCl3;	A 4.1% B 10.8%

tetrachlorosilane (10026-04-7, 53609-55-5) + dimethyldiphenylgermane (7301-42-0) → germaniumtetrachloride (10038-98-9) + phenyldimethylchlorogermane (22702-76-7) + methylphenylgermanium dichloride (25179-00-4)

Conditions	Yield
aluminium trichloride In solid Si-compound reacted with (CH3)2Ge(C6H5)2 at 110-120°C for 3 h in presence of AlCl3;	A 9.4% B 1.1% C 3%

Methyltrichlorosilane (75-79-6) + dimethyldiphenylgermane (7301-42-0) → germaniumtetrachloride (10038-98-9) + phenyldimethylchlorogermane (22702-76-7)

Conditions	Yield
aluminium trichloride In solid Si-compound reacted with (CH3)2Ge(C6H5)2 at 110-120°C for 3 h in presence of AlCl3;	A 1.1% B 7.4%

disulfur dichloride (10025-67-9) + germanium (7440-56-4) → germaniumtetrachloride (10038-98-9)

Conditions	Yield
In tetrahydrofuran addn. of 10-fold excess of S2Cl2 to Ge-atom/THF slurry (Ar atmosphere), stirring (50°C, 5 h); GC-MS, GLC;	6%

germanium (7440-56-4) + Bromotrichloromethane (75-62-7) → germanium tetrabromide (13450-92-5) + trichlorobromogermane (13536-49-7) + chlorotribromogermane (13536-71-5) + germaniumtetrachloride (10038-98-9)

Conditions	Yield
In gas vaporization of Ge (alumina-coated tungsten crucible, 1200-1300°C, 5E-3 Torr), introduction into flask (cooled with liq. N2 during Ge vaporization) together with vapor of org. halide, warming to room temp., standing for 1.5 h; further products; GC-MS, GLC;	A 0.7% B 0.6% C 0.6% D 5.8%

germanium (7440-56-4) + Bromotrichloromethane (75-62-7) → germanium tetrabromide (13450-92-5) + trichlorobromogermane (13536-49-7) + chlorotribromogermane (13536-71-5) + CCl3GeBrCl2 (113365-42-7) + germaniumtetrachloride (10038-98-9)

Conditions	Yield
reaction of germanium atoms with organic halide by co-condensation under vac. at 77 K; further products; GC-MASS;	A 0.7% B 1.1% C 0.6% D 0.6% E 5.8%

germanium (7440-56-4) + Bromotrichloromethane (75-62-7) → CCl3GeBr3 (113365-43-8) + germaniumtetrachloride (10038-98-9)

Conditions	Yield
In tetrahydrofuran addn. of 10-fold excess of BrCCl3 to Ge-atom/THF slurry (Ar atmosphere), stirring (50°C, 20 h); GC-MS, GLC;	A 3.5% B 1%
In tetrahydrofuran addn. of 10-fold excess of BrCCl3 to Ge-atom/THF slurry (Ar atmosphere), stirring (50°C, 5 h); GC-MS, GLC;	A 2.5% B 1%
In hexane addn. of 10-fold excess of BrCCl3 to Ge-atom/THF slurry (Ar atmosphere), stirring (50°C, 20 h); GC-MS, GLC;	A 1.5% B <1.0
In 1,2-dimethoxyethane addn. of 10-fold excess of BrCCl3 to Ge-atom/THF slurry (Ar atmosphere), stirring (50°C, 5 h); GC-MS, GLC;	A 1.5% B <1.0
In hexane addn. of 10-fold excess of BrCCl3 to Ge-atom/THF slurry (Ar atmosphere), stirring (50°C, 5 h); GC-MS, GLC;	A 1% B <1.0

germanium (7440-56-4) + phosphorus trichloride (7719-12-2, 52843-90-0) → germaniumtetrachloride (10038-98-9)

Conditions	Yield
In tetrahydrofuran addn. of 10-fold excess of PCl3 to Ge-atom/THF slurry (Ar atmosphere), stirring (50°C, 5 h); GC-MS, GLC;	2%

germanium (7440-56-4) + dichloromethane (75-09-2) → germaniumtetrachloride (10038-98-9) + trichloro(chloromethyl)germane (21572-18-9)

Conditions	Yield
In gas vaporization of Ge (alumina-coated tungsten crucible, 1200-1300°C, 5E-3 Torr), introduction into reaction flask (cooled with liq. N2 during Ge vaporization) together with vapor of org. halide, warming to room temp., standing for 1.5 h; GC-MS, GLC;	A 1.6% B 0.3%
reaction of germanium atoms with organic halide by co-condensation under vac. at 77 K; GC-MASS;	A 1.6% B 0.3%

tetramethylsilane (75-76-3) + germaniumtetrachloride (10038-98-9) → chloro-trimethyl-silane (75-77-4) + chlorotrimethylgermane (1529-47-1) + tetramethylgermane (865-52-1)

Conditions	Yield
aluminium bromide In neat (no solvent) molar ratio Me4Si/GeCl4 = 2/1, at 180°C for 2.75 h, cooled; NMR, mass spectra, chromy.;	A 100% B 18% C 82%
aluminium bromide In neat (no solvent) molar ratio Me4Si/GeCl4 = 2/1, at 180°C for 4.5 h, cooled; NMR, mass spectra, chromy.;	A 100% B 23% C 77%
aluminium bromide In neat (no solvent) molar ratio Me4Si/GeCl4 = 2/1, at 200°C for 3.5 h, cooled; NMR, mass spectra, chromy.;	A 100% B 13% C 87%

tetramethylsilane (75-76-3) + germaniumtetrachloride (10038-98-9) → chloro-trimethyl-silane (75-77-4) + chlorotrimethylgermane (1529-47-1) + dimethylsilicon dichloride (75-78-5)

Conditions	Yield
aluminium bromide In neat (no solvent) molar ratio Me4Si/GeCl4 = 2/1, at 200°C for 15 h, cooled; NMR, mass spectra, chromy.;	A 50% B 100% C 50%

tetramethylsilane (75-76-3) + germaniumtetrachloride (10038-98-9) → methyltrichlorogermane (993-10-2) + dimethylsilicon dichloride (75-78-5) + dichlorodimethylgermanium (1529-48-2)

Conditions	Yield
aluminium bromide In neat (no solvent) molar ratio Me4Si/GeCl4 = 0.5/1, at 200°C for 28 h, cooled; NMR, mass spectra, chromy.;	A 64% B 100% C 36%

tetramethylsilane (75-76-3) + germaniumtetrachloride (10038-98-9) → chlorotrimethylgermane (1529-47-1) + dimethylsilicon dichloride (75-78-5) + dichlorodimethylgermanium (1529-48-2)

Conditions	Yield
aluminium bromide In neat (no solvent) molar ratio Me4Si/GeCl4 = 1/1, at 200°C for 56 h, cooled; NMR, mass spectra, chromy.;	A 14% B 100% C 86%

germaniumtetrachloride (10038-98-9) + 1,3-bis(methylamino)propane (111-33-1) → C10H24Cl2GeN4

Conditions	Yield
With triethylamine	100%

ammonium sulfate + germaniumtetrachloride (10038-98-9) + disulfuric acid (7783-05-3) → GeO21S6(2-)*2H4N(1+)

Conditions	Yield
at 250℃; for 24h;	100%

germaniumtetrachloride (10038-98-9) + disulfuric acid (7783-05-3) + silver sulfate → GeO21S6(2-)*2Ag(1+)

Conditions	Yield
at 250℃; for 24h;	100%

germaniumtetrachloride (10038-98-9) + acrylonitrile (107-13-1) → 3-(trichlorogermyl)-propionitrile (68631-05-0)

Conditions	Yield
Stage #1: germaniumtetrachloride With 1,1,3,3-Tetramethyldisiloxane In diethyl ether for 1.5h; Reflux; Schlenk technique; Glovebox; Stage #2: acrylonitrile In diethyl ether for 20h; Schlenk technique; Glovebox;	100%

germaniumtetrachloride (10038-98-9) + dimethyl sulfoxide (67-68-5) → dimethyl sulfoxide, complex with tetrachlorogermane (2:1)

Conditions	Yield
In dichloromethane GeCl4 added dropwise with stirring to DMSO in CH2Cl2; ppt. filtered off, dried in vacuo; elem. anal.;	99%

1,1,3,3-Tetramethyldisiloxane (3277-26-7) + germaniumtetrachloride (10038-98-9) + methacrylic acid methyl ester (80-62-6) → methyl-β-trichlorogermyl-isobutyrate (95681-74-6)

Conditions	Yield
a mixt. of methyl methacrylate, 1,1,3,3-tetramethyldisiloxane and GeCl4 with an addition of Cl3GeH ether complex is kept at 20°C for about 5 d;; the product is isolated after cooling the mixt. to -20°C. By distn. of the mother soln. in a vacuum further product is obtained;;	99%

2-methylenesuccinic acid (97-65-4) + germaniumtetrachloride (10038-98-9) → diethyl [(trichlorogermyl)methyl]succinate (114686-96-3)

Conditions	Yield
With thionyl chloride; ethanol; hypophosphorous acid In ethanol mixt. of GeCl4 and H3PO2 (from NaH2PO2*7H2O and concd. HCl), boiled (14h, N2); addn. of itaconic acid at 0°C, extn. (room temp., CH2Cl2), ext. evapd. , residue dried (azeotropic method), iolated polymer boiled with SOCl2 (1 h), distn. with EtOH; excess SOCl2 distd. with ethanol (1 h); vac. distn.; elem. anal.;	99%

tetraphosphanylsilane (214424-22-3) + germaniumtetrachloride (10038-98-9) → tetraphosphanylgermane (214424-23-4) + Ge(PH2)Cl3 + Ge(PH2)2Cl2 + chlorotriphosphanylsilane (354136-21-3) + ClGe(PH2)3

Conditions	Yield
In tetrahydrofuran byproducts: PH3, HCl; 1:1 molar ratio, condensing at -196 °C, subsequently warming to room temp., 1 month, under Ar; a solid by-product was also formed, the product was dismutated into Cl2Si(PH2)2 and Cl3Si(PH2);	A 0% B 0% C 0% D 99% E 0%

(C2H5)3SnC(C6H5)2CO2CH3 + germaniumtetrachloride (10038-98-9) → Cl3GeC(C6H5)2CO2CH3 (185097-98-7)

Conditions	Yield
In neat (no solvent) byproducts: Et3SnCl; stirring (1 h); distn.;	99%

hexachlorodisilane (13465-77-5) + germaniumtetrachloride (10038-98-9) + tetraphenyl phosphonium chloride (2001-45-8) → Cl9GeSi3(1-)*C24H20P(1+)

Conditions	Yield
In dichloromethane at 20℃; for 12h;	99%
In dichloromethane at 20℃; for 12h;

1,1,3,3-Tetramethyldisiloxane (3277-26-7) + 10-undecenoic acid (112-38-9) + germaniumtetrachloride (10038-98-9) → 9-trichlorogermylundecanoic acid (127072-62-2)

Conditions	Yield
In neat (no solvent) mixt. kept 7 days at 20°C; pptn., liquid layer sepd. by decantation, crystals recrystn. (hexane);	98%

1,9-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-5-phenyldipyrrin (1312816-22-0) + germaniumtetrachloride (10038-98-9) → [(1,9-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-5-phenyldipyrrin(-3H))GeCl]

Conditions	Yield
With NaH In tetrahydrofuran 1,9-bis(2-hydroxyphenyl)dipyrrin deriv. treated with NaH in THF, treatment with GeCl4;	98%

ammonium hydroxide (1336-21-6) + dihydrogen peroxide (7722-84-1) + germaniumtetrachloride (10038-98-9) → Ge6H6O24(6-)*6H4N(1+)*6H2O

Conditions	Yield
pH=9;	97.2%

TMA-TPA + germaniumtetrachloride (10038-98-9) → CH3AlCl2*C9H21N + methyltrichlorogermane (993-10-2)

Conditions	Yield
at 40℃; for 3h;	A n/a B 97%

(E)-but-2-enoic acid (107-93-7) + 1,1,3,3-Tetramethyldisiloxane (3277-26-7) + germaniumtetrachloride (10038-98-9) → 3-(trichlorogermyl)butanoic acid (21187-26-8)

Conditions	Yield
In neat (no solvent) mixt. kept 12 days at 20°C (acid completely dissolved after 1 day, pptn. begins after 3 days); pptn., liquid layer sepd. by decantation, crystals recrystn. (hexane);	97%

1,3-bis-{3-(triethylgermyl)propyl}-5-(trimethylsilyl)-s-triazine-1,3,5(2H,4H,6H)-trione (112343-03-0) + germaniumtetrachloride (10038-98-9) → ClGe(C3(O)3N3((CH2)3Ge(C2H5)3)2)3 (112343-06-3)

Conditions	Yield
In neat (no solvent) byproducts: (CH3)3SiCl; mixt. of starting materials (molar ratio (3 (Si-compound):1 (GeCl4)) heated (2.5 h, at 80°C under Ar, 1 h at 150°C, 3 mm); elem. anal.;	97%

4-Ethylpyridine (536-75-4) + germaniumtetrachloride (10038-98-9) → bis(4-ethylpyridine)tetrachlorogermane (634899-88-0)

Conditions	Yield
In toluene (N2); GeCl4 was reacted with 4-ethylpyridine in toluene with stirring at 20°C; volatiles removed (vac.); elem. anal.;	97%

C35H36N2O2 (1619266-35-1) + germaniumtetrachloride (10038-98-9) → C35H33ClGeN2O2 (1619266-32-8)

Conditions	Yield
Stage #1: C35H36N2O2 With sodium hydride In tetrahydrofuran at 20℃; for 1.5h; Glovebox; Inert atmosphere; Stage #2: germaniumtetrachloride In tetrahydrofuran at 0 - 20℃; for 15h; Glovebox; Inert atmosphere;	97%

dipropyl styrenyl zirconacyclopentadiene + germaniumtetrachloride (10038-98-9) → C6H4C(C3H7)C(C3H7)GeCl2 (151176-28-2)

Conditions	Yield
In tetrahydrofuran byproducts: Cp2ZrCl2; under Ar; GeCl4 was added slowly to the Zr-compound at room temperature; stirring was maintained for 24 h; solvent was pumped away; residue was washed with pentane; extraction; solvent was removed; elem. anal.;	96%

C37H40N2O4 (1619266-31-7) + germaniumtetrachloride (10038-98-9) → C37H37ClGeN2O4 (1619266-27-1)

Conditions	Yield
Stage #1: C37H40N2O4 With sodium hydride In tetrahydrofuran at 20℃; for 1.5h; Glovebox; Inert atmosphere; Stage #2: germaniumtetrachloride In tetrahydrofuran at 0 - 20℃; for 15h; Glovebox; Inert atmosphere;	96%

tetrabutylgermanium (1067-42-1) + germaniumtetrachloride (10038-98-9) → tri-n-butylchlorogermane (2117-36-4)

Conditions	Yield
aluminium trichloride other Radiation; a mixt. of GeCl4 and tetraalkylgermane in presence of AlCl3 as catalystin a Pyrex tube is irradiated with a light stream of argon for 3 min atatmospheric pressure (microwave irradiation: 300 W) (Ar); identification by (1)H-NMR, gas chromy.;	95%

C6H4C(C2H5)C(C2H5)Zr(C5H5)2 + germaniumtetrachloride (10038-98-9) → C6H4C(C2H5)C(C2H5)GeCl2 (151176-27-1)

Conditions	Yield
In tetrahydrofuran byproducts: Cp2ZrCl2; under Ar; GeCl4 was added slowly to the Zr-compound at room temperature; stirring was maintained for 24 h; solvent was pumped away; residue was washed with pentane; extraction; solvent was removed; elem. anal.;	95%

germaniumtetrachloride (10038-98-9) + 1,3-diallyl-4-(trimethylsilyloxy)-2,6-dioxo-1,3,5-triazine (63226-47-1) → ClGe((NCO)3(CH2CHCH2)2)3

Conditions	Yield
In neat (no solvent) byproducts: Me3SiCl; mixt. heating (30-40 min, 120-160°C, distilling flask); exposition to vac. 1.33 hPa; elem. anal.;	95%

triethanolamine (102-71-6) + germaniumtetrachloride (10038-98-9) + phenylacetylene (536-74-3) → 1-(phenylethynyl)germatrane (72077-70-4)

Conditions

Yield

With Et3N; EtOH In ethanol; toluene (N2); standard Schlenk technique; flask with mixt. of C6H5CCH, GeCl4, Et3N in toluene was sealed, cooled, evacuated; heated at 110°C for 21 h; filtered; residue washed (toluene); EtOH and Et3N were added to filtrate and washings; mixt. stirred at; room temp. for 50 min; filtered; residue washed (toluene); filtrate and washings were added to (HOCH2CH2)3N; mixt. was stirred at 110°C for 6 h; cooled to room temp.; filtered; washed (pentane; CH2Cl2); solvent removed (vac.);

95%

N,N-dimethylhydroxylamine (5725-96-2) + germaniumtetrachloride (10038-98-9) → tetrakis(dimethylaminoxy)germane

Conditions	Yield
With n-butyl lithium In diethyl ether; hexane byproducts: LiCl; N,N-dimethylhydroxylamine dissolved in hexane; cooled to 0°C; soln. of n-BuLi in Et2O added dropwise; stirred for 1 h; GeCl4 added at 0°C; stirred for 0.5 h; refluxed for 1 h; cooled to 0°C; filtered; filtrate concd. in vac.; recrystd. from hexane; elem. anal.;	95%

Upstream product

• 7440-56-4 germanium 
• 7790-99-0 Iodine monochloride 
• 75-09-2 dichloromethane 
• 24422-23-9 GeCl₃[N(CH₃)2] 
• 75-78-5 dimethylsilicon dichloride 
• 7782-50-5 chlorine 
• 67-66-3 chloroform 
• 7719-12-2 phosphorus trichloride 
• 10025-67-9 disulfur dichloride 
• 7791-25-5 sulfuryl dichloride 
• 56-23-5 tetrachloromethane 
• 107-05-1 3-chloroprop-1-ene 
• 75-62-7 Bromotrichloromethane 
• 540-54-5 1-Chloropropane 

Downstream Products

• 96-10-6 diethylaluminium chloride 
• 993-42-0 ethyl germanium trichloride 
• 13892-14-3 2-Methyl-1-trichlorgermyl-propan 
• 865-52-1 tetramethylgermane 
• 13314-52-8 diethyl germanium dichloride 
• 597-63-7 tetraethylgermane 
• 993-10-2 methyltrichlorogermane 
• 651032-57-4 (1R,2S,5R)-(-)menthylgermanium trichloride 
• 1074-29-9 trichlorophenylgermane 
• 1613-66-7 dichlorodiphenylgermane 
• 7647-01-0 hydrogenchloride 
• 1033995-63-9 oxonium 
• 51594-04-8 Ge(OH)Cl₃ 
• 24847-51-6 ⁽²⁾H₃O⁽¹⁺⁾ 

Relevant articles and documents

Organotrichlorogermane synthesis by the reaction of elemental germanium, tetrachlorogermane and organic chloride via dichlorogermylene intermediate

Organotrichlorogermanes were synthesized by the reaction of elemental germanium, tetrachlorogermane and organic chlorides, methyl, propyl, isopropyl and allyl chlorides. Dichlorogermylene formed by the reaction of elemental germanium with tetrachlorogermane was the reaction intermediate, which was inserted into the carbon-chlorine bond of the organic chloride to give organotrichlorogermane. When isopropyl or allyl chloride was used as an organic chloride, organotrichlorogermane was formed also in the absence of tetrachlorogermane. These chlorides were converted to hydrogen chloride, which subsequently reacted with elemental germanium to give the dichlorogermylene intermediate. The reaction of elemental germanium, tetrachlorogermane and organic chlorides provides a simple and easy method for synthesizing organotrichlorogermanes, and all the raw materials are easily available.

Formation of Halide Complexes of Methyl- and Inorganic Germanium(IV) in Aqueous Hydrohalogenic Acid Solutions

The reaction of methyl- and inorganic germanium(IV) hydroxides ((CH3)nGe(OH)4-n; n = 1, 2, or 3) with halide ions (X = Cl-, Br-, or I-) to form halide complexes ((CH3)nGeX4-n) in aqueous acidic solution has been investigated by liquid-liquid extraction, solid-liquid distribution (ion exchange), and 1H NMR spectrometry.It has been found that methylgermanium moieties are hard Lewis acids similarly to inorganic germanium(IV), because the stability constant of the halide complexes decreases in the order Cl- > Br- > I-.The stability constant for an X- ion increases as the number of methyl groups attached to the germanium atom increases.The species of inorganic-, monomethyl-, and dimethylgermanium are nonionic and have a tetrahedral structure in HX solution, and OJ- ions attached to the germanium atom are stepwise substituted by X- ions with an increase in HX activity.Trimethylgermanium alone forms a cation, when the activity of HX is not sufficiently high.These facts suggest that the transfer of a negative charge from methyl groups to the central germanium atom lowers the stability of the bond between the germanium atom (hard acid) and an OH- ion (hard base).

Facile central-element exchange in neutral hexacoordinate germanium and silicon complexes; Synthesis and characterization of germanium complexes

Neutral hexacoordinate germanium complexes with hydrazido chelating ligands have been synthesized and characterized. Facile exchange of central element between silicon and germanium in these complexes is demonstrated, following given selectivity constrain

Direct synthesis of organotrichlorogermanes by the reaction of elemental germanium, hydrogen chloride, and alkene

The reaction of elemental germanium, hydrogen chloride, and ethylene with copper(I) chloride catalyst gave ethyltrichlorogermane with a 66% selectivity, tetrachlorogermane also being formed. The addition of tetrachlorogermane to the reaction system increased the formation rate of ethyltrichlorogermane. The reaction of germanium, tetrachlorogermane, and butadiene resulted in the formation of 1,1-dichlorogermacyclopent-3-ene. These results indicate the intermediacy of dichlorogermylene, which is formed by the reaction of elemental germanium with tetrachlorogermane. In place of ethylene, allyl chloride was fed with hydrogen chloride. Allyltrichlorogermane was obtained with a 92% selectivity together with a small amount of tetrachlorogermane. It is highly plausible that the formation of allyltrichlorogermane is caused by the insertion of dichlorogermylene intermediate to the carbon - chlorine bond of allyl chloride.

The chlorination equilibrium of germanium oxides

The reactions of tetragonal, hexagonal, and glassy GeO2 with chlorine were studied.From the measured equilibrium constants a third-law standard molar enthalpy of formation: ΔHf(GeCl4, g, 298.15 K, p0 = 101.325 kPa) = -(494.8 +/- 2.7) kJ*mol-1 was determined.

Reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride

The effect of substituents at the silicon and germanium atoms in reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride was studied. The only occurring process is the exchange of the chlorine atoms at Ge for the phenyl groups from Si; an increase in the number of methyl groups or chlorine atoms at Si promotes formation of phenyltrichlorogermane, and an increase in the number of phenyl groups or replacement of the chlorine atom at the Si atom by hydrogen leads to the formation of di-and triphenylchlorogermanes. Neither phenyl nor other radicals are transferred back from Ge to Si in the course of reactions of phenylgermanes with methylchlorosilanes in the presence of aluminum chloride; the only occurring processes are the exchange of the phenyl or methyl radicals bonded to Ge for the Cl atom bonded to Al and the disproportionation of phenylchlorogermanes. Nauka/Interperiodica 2006.

SO2 effect on GeO2 chlorination

The SO2 effect on the interaction of amorphous GeO2 with gaseous Cl2 in the temperature range 600-875°C is studied. The GeO2 chlorination rate in the presence of SO2 increases over the entire temperature range. The process rate is described as a function of temperature by a curve with a maximum at 720°C, which is due to the partial transition of amorphous GeO2 to the hexagonal phase.

Thermal transformations of phenyltrichlorogermane in the gas phase

Pyrolysis of PhGeCl3 and its mixtures with allyl chloride and isoprene in the temperature range 500-680°C was investigated. PhGeCl3 vigorously decomposes at temperatures higher 600°C, and its decomposition involves both dichlorogermylenes and trichlorogermyl radical. Pyrolysis of mixtures of PhGeCl3 with isoprene or allyl chloride yields respectively trichloro(1,2-dimethyl-2-propenyl)germane, isopentyltrichloro germanes, and 1,1-dichloro-3-methyl-1-germacyclo-3-pentene or allyltrichlorogermane. A mechanism of formation of these products is proposed.

Synthesis, structures and properties of N-(trihalogermylmethyl)-substituted amides, lactams and imides, the derivatives of the five-coordinate germanium

The formation of trichlorogermyl-substituted amides, lactams, and imides occurs when 2Et2O*HGeCl3 is condensed with compounds possessing the -NCH2Cl fragment and equally well when HGeCl3 interacts with compounds containing -NCH2OH and -NCH2OSiMe3 groups.I

Reactivity of Sulphuryl Chloride in Acetonitrile with the Elements

Sulphuryl chloride in MeCN reacts with all but the most refractory elements to give mainly solvated chlorides at or below 300 K in contrast with SO2Cl2 alone which requires at least twice this temperature.There is evidence for an ionic mechanism based on analogy, thermochemistry, transport measurements and additive effects.The instability of these solutions leading to polymerization, together with its inhibition, is described.Sulphur dioxide formed in reactions seldom plays a reductive role apart from influencing formation of the mixed-valence Tl4Cl6.Semiquantitative kinetic measurements in different solvents emphasize the uniqueness of MeCN.For most elements attack is diffusion controlled across surface films giving a parabolic dependence on time which can be linearized if film growth is prevented by changing the solvent mix.The varied nature of these surface films vitiates any simple relation between rate and periodicity.Some applications are indicated.