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首页> 外文期刊>Catalysis science & technology >Halide bridged trinuclear rhodium complexes and their inhibiting influence on catalysis
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Halide bridged trinuclear rhodium complexes and their inhibiting influence on catalysis

机译：卤化物桥接的三核铑配合物及其对催化的抑制作用

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摘要

The addition of halides to the cationic solvate complexes of the type [Rh(PP)(solvent)2][anion] leads to the formation of trinuclear μ3-halide-bridged complexes. The corresponding complexes [Rh3(PP)3(μ3-X)2][BF4] with X = CI or Br and diphosphines PP Me-DuPHOS, Et-DuPHOS, DIPAMP, t-Bu-BisP* and Tangphos were characterized - in most cases - also by X-ray analysis. By reducing the concentration of the active catalyst, the in situ formation of these μ-halide-bridged multinuclear complexes in catalytic reactions leads to a decrease in activity or even to a total inactivity. The required halides - in most cases chloride - are usually present as impurities in the substrates (also when produced industrially). The extent of deactivation, known from enzyme catalysis as competitive inhibition, depends on several factors: the type of halide, the ratio of stability constants of multinuclear halide complexes and of substrate complexes, and the concentration of halide and substrate in solution.
机译：在[RH（PP）（溶剂）2] [Anion]类型的阳离子溶剂化络合物中添加卤化物会导致形成三核μ3-卤化物桥接的复合物。 与X = CI或Br和Diphassphines Pp Me-Duphos，Et-Duphos，Dipamp，T-Bu-Bisp*和Tangphos的相应复合物[RH3（PP）3（pp）3（μ3-X）2] [BF4]在 大多数情况 - 也通过X射线分析。 通过降低活性催化剂的浓度，在催化反应中这些μ-甲化桥的多核复合物的原位形成会导致活性降低甚至完全不活跃。 所需的卤化物 - 在大多数情况下 - 氯化物 - 通常是底物中的杂质（也是工业生产时）。 失活的程度，从酶催化为竞争性抑制中已知，取决于几个因素：卤化物的类型，多核卤化物复合物的稳定性比例和底物复合物的稳定性比以及溶液中卤化物和底物的浓度。

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