SYNTHESES AND STRUCTURES OF GERMANIUM(II) AND GERMANIUM(IV) THIOLATE AND SELENOLATE COMPLEXES - [ET4N][GE(SPH)3], [PH4P][GE(SEPH)3], [PH4P]2[GE2(SCH2CH2S)3], GE(S-4-MEC6H4)4, AND GE(SE-2,4,6-ME3C6H2)4 - EXAMPLES OF THE 1ST 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(SCH2CH2S)3] (3) contain the first anionic germanium(II) complexes featuring trigonal pyramidal Ge(II)S3 or Ge(II)Se3 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 P2(1)/c with unit cell dimensions a = 18.374(4) angstrom, b = 9.052(2) angstrom, c = 17.595(4) angstrom, beta = 113.04(3)-degrees, V = 2693 angstrom3, and Z = 4 for 1 and = 10.665(3) angstrom, b = 17.204(4) angstrom, c = 20.345(6) angstrom, beta = 105.34(2); Z = 4, and V = 3616 angstrom3 for 2. The dinuclear complex 3 crystallizes from hot methanol in the triclinic space group P1BAR with a = 9.593(2) angstrom, b = 10.232(2) angstrom, c = 13.880(3) angstrom, alpha = 105.78(2)-degrees, beta = 91.90(2)-degrees, gamma = 106.62(2)-degrees, Z = 1, and V = 1247 angstrom3. The molecular anions of 1-3 contain stereochemically active Ge lone pairs, and bond angles at germanium are 87.6(1)-102.2(1)-degree (for 1 and 2) and 90.1(1)-100.9(1)-degree (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) angstrom, b = 16.325(3) angstrom, c = 19.962(3) angstrom, V = 5429 angstrom3, and Z = 8. 5 forms monoclinic crystals (space group P2(1)/n) with a = 12.627(4) angstrom, b = 21.803(6) angstrom, c = 13.119(4) angstrom, beta = 106.16(2)-degrees, V = 3469 angstrom3, and Z = 4. The mononuclear complexes with tetrahedrally coordinated germanium(IV) show slight distortions from ideal T(d) symmetry. The germanium(II) and germanium(IV) complexes are characterized by infrared and Raman spectroscopy.