Kinetics and mechanisms of the electron transfer reactions of oxo-centred carboxylate bridged complexes, [Fe<sub>3</sub>(µ<sub>3</sub>-O)(O<sub>2</sub>CR)<sub>6</sub>L<sub>3</sub>]ClO<sub>4</sub>, with verdazyl radicals in acetonitrile solution
作者:Lynette Keeney、Michael J. Hynes
DOI:10.1039/b418809h
日期:——
L. The kinetics of the electron transfer reaction observed when acetonitrile solutions of the complexes were reacted with a range of verdazyl radicals were monitored using stopped-flow spectrophotometry. Under the experimental conditions, the reactions were quite rapid and were monitored under second-order conditions. Marcus linear free energy plots indicated that the outer-sphere electron transfer
范围为通式[Fe 3(µ 3 -O)(O 2 CR)6 L 3 ] ClO 4 (R = CH 2 CN,CH 2 F,CH 2 Cl的以氧为中心的,羧酸根桥联的三铁配合物,CH 2 Br,p -NO 2 C 6 H 4; L =吡啶, 3-甲基吡啶, 4-甲基吡啶, 3,5-二甲基吡啶, 3-氰基吡啶 和 3-氟吡啶)已准备好并进行了特征化。R和L的选择是由这样的要求决定的,即配合物与凡达唑基反应时,该配合物会发生单电子还原。除L =的复数以外的所有复数吡啶R = CH 2 CN,CH 2 Cl和p -NO 2 C 6 H 4尚未见报道。这些化合物的氧化还原行为已使用循环伏安法 在 乙腈通常,所有络合物均表现出可逆的单电子还原。在过量L的存在下,电化学行为得到改善。乙腈 使配合物溶液与一定范围的Verdazyl自由基反应,并使用停止流进行监测 分光光度法。在实验条件下,反应相当快,并且在