99901-40-3Relevant academic research and scientific papers
Synthesis and molecular structure of five-coordinated phenyl-substituted anionic germanium(IV) complexes. Influence of the central atom on geometry
Holmes, Robert R.,Day, Roberta O.,Sau, Arjun C.,Poutasse, Charles A.,Holmes, Joan M.
, p. 607 - 611 (2008/10/08)
A series of pentacoordinated phenyl-substituted anionic germanates, 1-4, were synthesized from phenylgermanium trichloride and a catechol or thiocatecho] ligand in the presence of a base: [(C6H4O2)2GePh] [Et4N] (1); [(C6H4O2)2GePh][Et 3NH]·1/6CH3CN (2); [(C6Cl4O2)2GePh][Et4N] (3); [(C6H4OS)2GePh][Ph4As] (4). The ethanedithiolato derivative [(C2H4S2)2GePh][Et4N] (5) also was synthesized. The X-ray structure of 1 is midway between a trigonal bipyramid and rectangular pyramid while 2 and 3 are more nearly rectangular pyramidal. Hydrogen bonding influences the structure of 2. Electron withdrawal by the ring chlorine atoms rationalizes the structural displacement found for 3. Comparisons with related structures of phenyl-substituted penta-coordinated derivatives of silicon, phosphorus, arsenic, and antimony show an increasing ease of solid-state distortion toward the rectangular pyramid as the electronegativity of the central atom is decreased: Ge > Si in group 4(14) and Sb > As > P in group 5 (15). 1 crystallizes in the monoclinic space group P21/n with a = 10.096 (3) A?, b = 22.724 (6) A?, c = 10.985 (1) A?, β = 102.65 (2)°, and Z = 4. 2 crystallizes in the trigonal space group R3 with aH = 23.666 (7) A?, cH = 21.967 (4) A?, and Z = 18. 3 crystallizes in the monoclinic space group P21/n with a = 8.591 (2) A?, b = 20.979 (6) A?, c = 17.367 (3) A?, β = 90.29 (2)°, and Z = 4. The final conventional unweighted residuals were 0.033 (1), 0.059 (2), and 0.048 (3).
