22555-00-6Relevant articles and documents
Electron transfer. 144. Reductions with germanium(II)
Babich, Olga A.,Gould, Edwin S.
, p. 4119 - 4122 (2008/10/08)
Solutions 0.2-0.4 M in Ge(II) and 6 M in HCl, generated by reaction of Ge(IV) with H3PO2, are stable for more than 3 weeks and can be diluted 200-fold with dilute HCl to give GeCl3- preparations to be used in redox studies. Kinetic profiles for the reduction of Fe(III) by Ge(II), as catalyzed by Cu(II), implicate the odd-electron intermediate, Ge(III), which is formed from Cu(II) and Ge(II) (k = 30 M-1 s-1 in 0.5 M HCl at 24 °C) and which is consumed by reaction with Fe(III) (k = 6 x 102 M-1 s-1). A slower direct reaction between Ge(II) and Fe(III) (k = 0.66 M-1 s-1) can be detected in 1.0 M HCl. The reaction of Ge(II) with I3- in 0.01-0.50 M iodide is zero order in oxidant and appears to proceed via a rate-determining heterolysis of a Ge(II)-OH2 species (k = 0.045 s-1) which is subject to H+-catalysis. Reductions of IrCl62- and PtCl62- by Ge(II) are strongly Cl--catalyzed. The Ir(IV) reaction proceeds through a pair of 1e- changes, of which the initial conversion to Ge(III) is rate-determining, whereas the Pt(IV) oxidant probably utilizes (at least in part) an inner-sphere Pt(IV)-Cl-Ge(II) bridge in which chlorine is transferred (as Cl+) from oxidant to reductant. The 2e- reagent, Ge(II), like its 5s2 counterpart, In(I), can partake in 1e- transactions, but requires more severe constraints: the coreagent must be more powerfully oxidizing and the reaction medium more halide-rich.
New Reactions of Precious Metals and their Binary Compounds in Solvents containing Carbon Halides
Jackson, Neale R. C.,Harrison, W. David,Goodall, David C.
, p. 729 - 730 (2007/10/02)
Several precious metals and binary compounds react with CCl4, CBr4, CPh2Cl2, CPhCl3, or C(CN)2Cl2 in dimethyl sulphoxide, dimethylformamide, or dimethylacetamide, and with carbon halides in ethanol or acetaldehyde containing added ligand.
