Reaction of metals with benzenediazonium tetrafluoroborate in aprotic solvents

摘要

The reaction of metals and glassy carbon with benzenediazonium tetrafluoroborate (BDFB) in aprotic solvents has been studied. During contact of Pt, Au, Ag, Pd, or V with glassy carbon in concentrated diazonium salt solution no change of color was observed. For Al, Ca, Cr, Cu, Fe, Ga, In, Mg, Li, Na, or Zn the process was accompanied by a rapid solution color change, rapid N2 release and the loss of metal sample mass. The copper metal ionization-dissolution was studied by ultraviolet and visible absorption spectroscopy, along with gravimetric and volumetric measurements. A dissolution mechanism was proposed based on kinetic, infrared, and X-ray diffraction data. The 432 nm absorption band appearing after Cu-BDFB reaction indicates formation of the mixed complex [Cu(N2C6H5 · (N≡C-CH3)3)~+ where the copper atom is covalently bonded to the azophenyl radical and coordinated to acetonitrile (ACN). This complex is thermodynamically unstable and decomposes slowly to a colorless crystalline and a black amorphous phase. The crystalline phase was identified as [Cu(NC-CH3)4]BF4. The amorphous phase is a mixture of products formed by azophenyl and phenyl radical condensation.