Germanium dichloride dioxane

Last updated
Germanium dichloride dioxane
GeCl2dioxane.svg
Identifiers
3D model (JSmol)
EC Number
  • 608-226-7
PubChem CID
  • InChI=1S/C4H8O2.Cl2Ge/c1-2-6-4-3-5-1;1-3-2/h1-4H2;
    Key: NYMJLNHIEKAQSD-UHFFFAOYSA-N
  • C1COCCO1.Cl[Ge]Cl
Properties
C4H8Cl2GeO2
Molar mass 231.64 g·mol−1
Appearancewhite solid
Density 1.942 g/cm3
Hazards
GHS labelling: [1]
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg
Warning
H314, H332, H351
P203[ ? ], P260, P261, P264, P271, P280, P301+P330+P331, P302+P361+P354[ ? ], P304+P340, P305+P354+P338[ ? ], P316, P317[ ? ], P318[ ? ], P321, P363, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Germanium dichloride dioxane is a chemical compound with the formula GeCl2(C4H8O2), where C4H8O2 is 1,4-dioxane. It is a white solid. The compound is notable as a source of Ge(II), which contrasts with the pervasiveness of Ge(IV) compounds. This dioxane complex represents a well-behaved form of germanium dichloride.

Contents

Synthesis and structure

It is prepared by reduction of a dioxane solution of germanium tetrachloride with tributyltin hydride: [2]

GeCl4 + 2 Bu3SnH + C4H8O2 → GeCl2(O2C4H8) + 2 Bu3SnCl + H2

Hydrosilanes have also been used as reductants. [3]

The complex has a polymeric structure. Germanium adopts an SF4-like shape with cis Cl ligands (Cl-Ge-Cl angle = 94.4°) and axial positions occupied by oxygen provided by a bridging dioxane. The Ge-O and Ge-Cl distances are 2.40 and 2.277 A, respectively. [4]

Reactions

The complex is used in the preparation of organogermanium compounds. [5] [6] In organic synthesis, the complex is used as a Lewis acid with reducing properties. [3]

Related Research Articles

<span class="mw-page-title-main">Oxalyl chloride</span> Chemical compound

Oxalyl chloride is an organic chemical compound with the formula (COCl)2. This colorless, sharp-smelling liquid, the diacyl chloride of oxalic acid, is a useful reagent in organic synthesis.

<span class="mw-page-title-main">Organotin chemistry</span> Branch of organic chemistry

Organotin compounds or stannanes are chemical compounds based on tin with hydrocarbon substituents. Organotin chemistry is part of the wider field of organometallic chemistry. The first organotin compound was diethyltin diiodide, discovered by Edward Frankland in 1849. The area grew rapidly in the 1900s, especially after the discovery of the Grignard reagents, which are useful for producing Sn–C bonds. The area remains rich with many applications in industry and continuing activity in the research laboratory.

<span class="mw-page-title-main">McMurry reaction</span>

The McMurry reaction is an organic reaction in which two ketone or aldehyde groups are coupled to form an alkene using a titanium chloride compound such as titanium(III) chloride and a reducing agent. The reaction is named after its co-discoverer, John E. McMurry. The McMurry reaction originally involved the use of a mixture TiCl3 and LiAlH4, which produces the active reagents. Related species have been developed involving the combination of TiCl3 or TiCl4 with various other reducing agents, including potassium, zinc, and magnesium. This reaction is related to the Pinacol coupling reaction which also proceeds by reductive coupling of carbonyl compounds.

Boron trichloride is the inorganic compound with the formula BCl3. This colorless gas is a reagent in organic synthesis. It is highly reactive toward water.

<span class="mw-page-title-main">Titanocene dichloride</span> Chemical compound

Titanocene dichloride is the organotitanium compound with the formula (η5-C5H5)2TiCl2, commonly abbreviated as Cp2TiCl2. This metallocene is a common reagent in organometallic and organic synthesis. It exists as a bright red solid that slowly hydrolyzes in air. It shows antitumour activity and was the first non-platinum complex to undergo clinical trials as a chemotherapy drug.

<span class="mw-page-title-main">Grignard reagent</span> Organometallic compounds used in organic synthesis

A Grignard reagent or Grignard compound is a chemical compound with the general formula R−Mg−X, where X is a halogen and R is an organic group, normally an alkyl or aryl. Two typical examples are methylmagnesium chloride Cl−Mg−CH3 and phenylmagnesium bromide (C6H5)−Mg−Br. They are a subclass of the organomagnesium compounds.

Vanadium tetrachloride is the inorganic compound with the formula VCl4. This bright red liquid serves as a useful reagent for the preparation of other vanadium compounds.

<span class="mw-page-title-main">Zeise's salt</span> Chemical compound

Zeise's salt, potassium trichloro(ethylene)platinate(II), is the chemical compound with the formula K[PtCl3(C2H4)]·H2O. The anion of this air-stable, yellow, coordination complex contains an η2-ethylene ligand. The anion features a platinum atom with a square planar geometry. The salt is of historical importance in the area of organometallic chemistry as one of the first examples of a transition metal alkene complex and is named for its discoverer, William Christopher Zeise.

<span class="mw-page-title-main">Methyllithium</span> Chemical compound

Methyllithium is the simplest organolithium reagent with the empirical formula CH3Li. This s-block organometallic compound adopts an oligomeric structure both in solution and in the solid state. This highly reactive compound, invariably used in solution with an ether as the solvent, is a reagent in organic synthesis as well as organometallic chemistry. Operations involving methyllithium require anhydrous conditions, because the compound is highly reactive toward water. Oxygen and carbon dioxide are also incompatible with MeLi. Methyllithium is usually not prepared, but purchased as a solution in various ethers.

<span class="mw-page-title-main">Titanocene dicarbonyl</span> Chemical compound

Dicarbonylbis(cyclopentadienyl)titanium is the chemical compound with the formula (η5-C5H5)2Ti(CO)2, abbreviated Cp2Ti(CO)2. This maroon-coloured, air-sensitive species is soluble in aliphatic and aromatic solvents. It has been used for the deoxygenation of sulfoxides, reductive coupling of aromatic aldehydes and reduction of aldehydes.

Niobocene dichloride is the organometallic compound with the formula (C5H5)2NbCl2, abbreviated Cp2NbCl2. This paramagnetic brown solid is a starting reagent for the synthesis of other organoniobium compounds. The compound adopts a pseudotetrahedral structure with two cyclopentadienyl and two chloride substituents attached to the metal. A variety of similar compounds are known, including Cp2TiCl2.

<span class="mw-page-title-main">Trimethyltin chloride</span> Chemical compound

Trimethyltin chloride is an organotin compound with the formula (CH3)3SnCl. It is a white solid that is highly toxic and malodorous. It is susceptible to hydrolysis.

<span class="mw-page-title-main">Tetramethyltin</span> Chemical compound

Tetramethyltin is an organometallic compound with the formula (CH3)4Sn. This liquid, one of the simplest organotin compounds, is useful for transition-metal mediated conversion of acid chlorides to methyl ketones and aryl halides to aryl methyl ketones. It is volatile and toxic, so care should be taken when using it in the laboratory.

<span class="mw-page-title-main">Germanium dichloride</span> Chemical compound

Germanium dichloride is a chemical compound of germanium and chlorine with the formula GeCl2. It is a yellow solid. Germanium dichloride is an example of a compound featuring germanium in the +2 oxidation state.

<span class="mw-page-title-main">Selenium monochloride</span> Chemical compound

Selenium monochloride is an inorganic compound with the formula Se2Cl2. Although it is called selenium monochloride, a more descriptive name might be diselenium dichloride. It is a reddish-brown, oily liquid that hydrolyses slowly. It exists in chemical equilibrium with SeCl2, SeCl4, chlorine, and elemental selenium. Selenium monochloride is mainly used as a reagent for the synthesis of Se-containing compounds.

In organometallic chemistry, bent metallocenes are a subset of metallocenes. In bent metallocenes, the ring systems coordinated to the metal are not parallel, but are tilted at an angle. A common example of a bent metallocene is Cp2TiCl2. Several reagents and much research is based on bent metallocenes.

<span class="mw-page-title-main">Dicarbonyl(acetylacetonato)rhodium(I)</span> Chemical compound

Dicarbonyl(acetylacetonato)rhodium(I) is an organorhodium compound with the formula Rh(O2C5H7)(CO)2. The compound consists of two CO ligands and an acetylacetonate. It is a dark green solid that dissolves in acetone and benzene, giving yellow solutions. The compound is used as a precursor to homogeneous catalysts.

<span class="mw-page-title-main">Phenyl(trichloromethyl)mercury</span> Chemical compound

Phenyl(trichloromethyl)mercury is an organomercury compound with the formula C6H5HgCCl3. It is a white solid that is soluble in organic solvents. The compound is used as a source of dichlorocarbene, e.g. in cyclopropanation reactions, illustrated with tetrachloroethylene as a substrate, the product being hexachlorocyclopropane:

<span class="mw-page-title-main">(Benzene)ruthenium dichloride dimer</span> Chemical compound

(Benzene)ruthenium dichloride dimer is the organoruthenium compound with the formula [(C6H6)RuCl2]2. This red-coloured, diamagnetic solid is a reagent in organometallic chemistry and homogeneous catalysis.

Niobium(III) chloride also known as niobium trichloride is a compound of niobium and chlorine. The binary phase NbCl3 is not well characterized but many adducts are known.

References

  1. "Germanium(II) chloride dioxane complex (1:1)". pubchem.ncbi.nlm.nih.gov.
  2. Fjeldberg, Torgny; Haaland, Arne; Schilling, Birgitte E. R.; Lappert, Michael F.; Thorne, Andrew J. (1986). "Subvalent Group 4B Metal Alkyls and Amides. Part 8. Germanium and Tin Carbene Analogues MR2[M = Ge or Sn, R = CH(SiMe3)2]: Syntheses and Structures in the Gas Phase (Electron Diffraction); Molecular-Orbital Calculations for MH2 and GeMe2". Journal of the Chemical Society, Dalton Transactions (8): 1551. doi:10.1039/DT9860001551.
  3. 1 2 Roskamp, Carrie A.; Roskamp, Eric J. (2001). "Germanium Dichloride-Dioxane Complex". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rg002. ISBN   0471936235.
  4. Leites, L.A.; Zabula, A.V.; Bukalov, S.S.; Korlyukov, A.A.; Koroteev, P.S.; Maslennikova, O.S.; Egorov, M.P.; Nefedov, O.M. (2005). "Experimental and Theoretical Study of Vibrational Spectra and Structure of Dihalogermylene and Dihalostannylene Complexes with 1,4-Dioxane and Triphenylphosphine". Journal of Molecular Structure. 750 (1–3): 116–122. Bibcode:2005JMoSt.750..116L. doi:10.1016/j.molstruc.2005.04.015.
  5. Simons, Richard S.; Pu, Lihung; Olmstead, Marilyn M.; Power, Philip P. (1997). "Synthesis and Characterization of the Monomeric Diaryls M{C6H3-2,6-Mes2}2 (M = Ge, Sn, or Pb; Mes = 2,4,6-Me3C6H2−) and Dimeric Aryl−Metal Chlorides [M(Cl){C6H3-2,6-Mes2}]2 (M = Ge or Sn)". Organometallics. 16 (9): 1920–1925. doi:10.1021/OM960929L.
  6. Roskamp, Carrie A.; Roskamp, Eric J. (2001). "Germanium Dichloride-Dioxane Complex". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rg002. ISBN   0471936235.