MECHANISM OF THE REACTIONS OF OXOMOLYBDENUM(V) TETRAPHENYLPORPHYRIN COMPLEX WITH ALCOHOLS IN THE PRESENCE OF SUPEROXIDE.

Article abstract of DOI:10.1246/bcsj.57.194

The successive addition of ROH (R equals CH//3 and C//2H//5) to the dichloromethane solution of Mo**vO(tpp)Br (tpp equals meso-tetraphenylporphinato) causes two-step reactions at 25 degree C. The products of the first and the second step of the reactions are alcohol complex, left bracket Mo**vO(tpp)(ROH) right bracket Br, and alkoxo complex, Mo**vO(tpp)OR, respectively. In the presence of superoxide ion, O//2** minus , in the dichloromethane solution of Mo**vO(tpp)X (X equals Br and NCS) containing alcohol, Mo**vO(tpp)OR is formed through competitive two reaction paths where O//2** minus acts as a proton acceptor and a reducing agent. The reaction steps of the two paths were confirmed by optical and ESR studies.