Cervilla Antonio, Pérez-Pla Francisco, Llopis Elisa, Piles María
ICMUV, P.O. Box 2085, Polígono La Coma, Paterna, Valencia 46071, Spain.
Inorg Chem. 2005 Jun 13;44(12):4106-8. doi: 10.1021/ic0483242.
Mo(VI)(S(2)C(6)H(4))(3) reacts cleanly and completely with H(2)O in THF to afford H(3)OMo(V)(S(2)C(6)H(4))(3). Kinetic data were fit by the rate equation -d[Mo(VI)(S(2)C(6)H(4))(3)]/dt = k[Mo(VI)(S(2)C(6)H(4))(3)]/[H(3)O(+)], which is consistent with a coupled electron-proton transfer mechanism involving a coordinated H(2)O molecule. The Mo(VI)(S(2)C(6)H(4))(3) reduction is accelerated by the presence of PPh(3) and affords OPPh(3). (18)O isotope tracing shows that H(2)O is the source of oxygen transferred to PPh(3).
Mo(VI)(S₂C₆H₄)₃在四氢呋喃中与水完全且顺利地反应，生成[H₃O]⁺[Mo(V)(S₂C₆H₄)₃]⁻。动力学数据通过速率方程-d[Mo(VI)(S₂C₆H₄)₃]/dt = k[Mo(VI)(S₂C₆H₄)₃]/[H₃O⁺]拟合，这与涉及配位水分子的耦合电子-质子转移机制一致。三苯基膦（PPh₃）的存在加速了Mo(VI)(S₂C₆H₄)₃的还原反应，并生成氧化三苯基膦（OPPh₃）。¹⁸O同位素示踪表明，水是转移到三苯基膦上的氧的来源。
