Thermal decomposition of covalent derivatives of tri- and tetravalent vanadium

R3V and R4V (R=CH2Ph, CH2SiMe3, C6F5) thermal decomposition is studied. Specific peculiarities of this process depending on the nature of σ-substitute, vanadium atom valency and medium conditions are found. Pentafluorophenyl derivatives prove to be most thermally stable in the series of compounds studied. The mechanism of benzyl and trimethylsilylmethyl derivatives in the solid state and in solutions are suggested. The homolytic splitting of σ-bond V-C and the following R-radical transformation into RH are considered. σ-substitute nature, the coordination environment of the central atom and the possibility of reconstructing the electron configuration of the central atom in the decomposition process are the decisive factors which determine the direction of decomposition of vanadium organic compounds