Reactivity of an adsorbed Ru(VI)-oxo complex: oxidation of benzyl alcohol.
Reactivity of an adsorbed Ru(VI)-oxo complex: oxidation of benzyl alcohol.
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吸附的 Ru(VI)-氧配合物的反应性：苯甲醇的氧化。
DOI：
10.1021/ic0700506
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发表时间：
2007
影响因子：
4.6
通讯作者：
T. Meyer
中科院分区：
文献类型：
--
作者：
Brooks J. Hornstein;D. Dattelbaum;J. Schoonover;T. Meyer
合成了一种膦配体钌配合物[Ru（tpy-PO（3）H（2））（OH（2））（3）]（2+）（1）（tpy-PO（3）H（2）= 4 '-膦酸基-2，2'：6 '，2“'-三联吡啶），并将其固定在玻璃上|ITO或玻璃|ITO| TiO（2）电极。在通过膦酸酯键连接到金属氧化物表面后，1可以被氧化（化学或电化学）成反应性Ru（VI）-二氧代络合物，玻璃|ITO| [（（HO）（2）OP）tpy）RuVI（O）（2）（OH（2））]（2+），其保持附着于表面。所附的Ru（VI）配合物与苯甲醇反应，通过类似的机制提出的解决方案类似。更具体地，Ru（VI）以逐步的方式还原为Ru（IV），然后最终还原为Ru（II）。Ru（VI）的还原伴随着对苯甲醇的C-H键的限速插入，接着是醛水合物的溶剂分解。此外，表面结合的Ru（VI）充当电氧化催化剂，在失活之前进行大约130次（2 e（-））翻转。
The phosphonated ruthenium complex, [Ru(tpy-PO(3)H(2))(OH(2))(3)](2+) (1) (tpy-PO(3)H(2) = 4'-phosphonato-2,2':6',2' '-terpyridine), was synthesized and attached to glass|ITO or glass|ITO|TiO(2) electrodes. After attachment to the metal oxide surface through the phosphonate linkage, 1 can be oxidized (either chemically or electrochemically) to the reactive Ru(VI)-dioxo complex, glass|ITO|[((HO)(2)OP)tpy)RuVI(O)(2)(OH(2))](2+), which remains attached to the surface. The attached Ru(VI) complex reacts with benzyl alcohol through mechanisms similar to those proposed for the solution analog. More specifically, Ru(VI) is reduced in a stepwise fashion to Ru(IV) and then finally to Ru(II). The reduction of Ru(VI) is accompanied by a rate-limiting insertion to the C-H bond of benzyl alcohol, followed by solvolysis of the aldehyde hydrate. In addition, the surface-bound Ru(VI) acts as an electrooxidation catalyst which carries out approximately 130 (2e(-)) turnovers before deactivation.