Germanium dichloride dioxane

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.

Germanium dichloride dioxane
Identifiers
3D model (JSmol)
EC Number
  • 608-226-7
  • 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
Appearance white solid
Density 1.942 g/cm3
Hazards
GHS labelling:[1]
GHS05: CorrosiveGHS07: Exclamation markGHS08: Health hazard
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).
Infobox references

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]

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. 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.
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