12307-22-1Relevant articles and documents
Electrochemical synthesis and properties of (η5-C5H4R)2TiSe5 (R = H, Me, i-Pr)
Tainturier,Gautheron,Degrand
, p. 942 - 946 (2008/10/08)
Ultrasound-induced electrochemical reduction of gray Se powder in DMF or THF, followed by addition of (η5-C5H4R)2TiCl2 (1, R = H, i-Pr), led to (η5-C5H4R)2TiSe5 (2, R = H, i-Pr) in high current efficiencies in THF and low to moderate yields in DMF. Compounds 2 could be also prepared in moderate yields when 1 was reduced at a Pt cathode in THF, in the presence of an excess of Se (at least 5 equiv). Finally, 2 was obtained in low yields when 1 was chemically reduced to the dimeric form (η5-C5H4R)2TiCl (3), gray Se powder being added after reduction. From the electrochemical results, it is suggested that a key step of the overall process leading to 2 is a one-electron reduction of complex 1, followed by formation of complex 3. In the first electrochemical method, an homogeneous electron transfer would occur between an electrochemically generated Se anionic species and complex 1. The lower yields of 2 in DMF than in THF are in agreement with the better binding properties of DMF, compared to THF, as far as complex 3 is concerned. Complexes 2 were irreversibly reduced and worked as a soluble Se reservoir. The electrochemical synthesis of 2 (R = Me) was thus achieved in 70% yield.
