1111084-48-0Relevant academic research and scientific papers
Syntheses and structures of germanium(II) and germanium(IV) thiolate and selenolate complexes: [Et4N][Ge(SPh)3], [Ph4P][Ge(SePh)3], [Ph4P]2[Ge2(SCH2CH 2S)3], Ge(S-4-MeC6H4)4, and Ge(Se-2,4,6-Me3C6H ...
Kersting, Berthold,Krebs, Bernt
, p. 3886 - 3892 (2008/10/08)
Full title: Syntheses and structures of germanium(II) and germanium(IV) thiolate and selenolate complexes: [Et4N][Ge(SPh)3], [Ph4P][Ge(SePh)3], [Ph4P]2[Ge2(SCH2CH 2S)3], Ge(S-4-MeC6H4)4, and Ge(Se-2,4,6-Me3C6H2)4. Examples of the first anionic germanium(II) complexes containing the trigonal pyramidal GeIIS3 and GeIISe3 cores. A series of germanium(II) thiolato and selenolato complexes were prepared by metathesis reactions of germanium dibromide with the sodium salts of benzenethiol, benzeneselenol, and ethanedithiol in mixed diethyl ether-methanol solutions. The crystalline products [Et4N][Ge(SPh)3] (1), [Ph4P][Ge(SePh)3] (2), and [Ph4P]2[Ge2(SCH2CH 2S)3] (3) contain the first anionic germanium(II) complexes featuring trigonal pyramidal GeIIS3 or GeIISe3 cores, and all were structurally characterized by X-ray crystallography. Both 1 and 2 crystallize from hot methanol or acetonitrile in the monoclinic space group P21/c with unit cell dimensions a = 18.374(4) ?, b = 9.052(2) ?, c = 17.595(4) ?, β = 113.04(3)°, V = 2693 ?3, and Z = 4 for 1 and a = 10.665(3) ?, b = 17.204(4) ?, c = 20.345(6) ?, β = 105.34(2)°, Z = 4, and V = 3616 ?3 for 2. The dinuclear complex 3 crystallizes from hot methanol in the triclinic space group P1 with a = 9.593(2) ?, b = 10.232(2) ?, c = 13.880(3) ?, α = 105.78(2)°, β = 91.90(2)°, γ = 106.62(2)°, Z = 1, and V = 1247 ?3. The molecular anions of 1-3 contain stereochemically active Ge lone pairs, and bond angles at germanium are 87.6(1)-102.2(1)° (for 1 and 2) and 90.1(1)-100.9(1)° (for 3). The tetrahedrally coordinated germanium(IV) derivatives Ge(S-4-MeC6H4)4 (4) and Ge(Se-2,4,6-Me3C6H2)4 (5) were also synthesized and structurally characterized: Orthorhombic 4 crystallizes in the space group Pbca with a = 16.660(2) ?, b = 16.325(3) ?, c = 19.962(3) ?, V = 5429 ?3, and Z = 8. 5 forms monoclinic crystals (space group P21/n) with a = 12.627(4) ?, b = 21.803(6) ?, c = 13.119(4) ?, β = 106.16(2)°, V = 3469 ?3, and Z = 4. The mononuclear complexes with tetrahedrally coordinated germanium(IV) show slight distortions from ideal Td symmetry. The germanium(II) and germanium(IV) complexes are characterized by infrared and Raman spectroscopy.
