By István T. Horváth, Ferenc Joó
Within the final 15 years aqueous organometallic chemistry and catalysis has emerged from being a laboratory interest to turn into a longtime box of study. issues reviewed right here contain mechanistic experiences at the influence of water on catalyzed reactions, the coaching of water soluble phosphines as ligands for catalysis, steel catalyzed natural reactions in water (hydrogenation, hydroformylation, carbonylation, olefin metathesis, hydrophosphination, etc.), chiral ligands and enantioselective catalysis, organometallic radical photochemistry in aqueous strategies, bioorganometallic chemistry, organometallic reactions of biopolymers, and catalytic amendment of biomembranes. The precis of contemporary effects is supplemented via an evaluate of possible destiny learn tendencies.
Audience: Researchers in either academia and undefined, in addition to graduate scholars of homogeneous catalysis.
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Extra info for Aqueous Organometallic Chemistry and Catalysis
3. Water Stable Metathesis Catalysts Since it was observed that an extremely active catalyst could be prepared in extremely low yield from Ru(II) and a strained olefin and that this catalyst was tolerant of a variety of functionality as wen as water, routes to a welldefined ruthenium car bene complex were explored since it was anticipated that such a complex would be particularly tolerant of functionality and processing conditions. It was found that the reaction of a simple ruthenium carbene complex, tetrakistriphenylphosphinerutheniumdichloride, with dipheny1cyclopropene (one of the most strained olefins available) resulted in the generation of a stable carbene complex .
I~~ - +_PMe, . Ir_ PM CI e3 PMe3 I (1) 1 precipitates in nearly quantitative yield when the reaction is carried out in toluene3. The structure of 1 is square pyramidal in the solid state, although it is fluxional in solution. 8 M in iridium. 1 is also quite basic and is readily protonated on iridium. 0 which indicates that 1 is approximately as basic as pyridine. Reaction between 1 and pyridinium chloride in water results in the eqUilibrium shown in equation 2. An eqUilibrium 33 I. T. Horvath and F.
The bulk of the activity directed toward developing watersoluble catalysts centers around modifying currently used ligands, such as triphenylphosphine, to make them water soluble!. In turn, attachment of these now water-soluble ligands imparts water solubility to the metal complex catalyst. Systems in which the aqueous solubility of an organometallic catalyst is not dependent on the attachment of a water-soluble ligand are not as well known 2. In this paper, we report on the aqueous chemistry and catalytic activity of some organometallic iridium complexes.
Aqueous Organometallic Chemistry and Catalysis by István T. Horváth, Ferenc Joó